U.S. patent application number 10/524807 was filed with the patent office on 2006-06-08 for process for preparing paste-extruded sulfonamide compositions.
Invention is credited to JosepheJ Keenan, LuannM Pugh, RobertT Roche.
Application Number | 20060122060 10/524807 |
Document ID | / |
Family ID | 31997917 |
Filed Date | 2006-06-08 |
United States Patent
Application |
20060122060 |
Kind Code |
A1 |
Keenan; JosepheJ ; et
al. |
June 8, 2006 |
Process for preparing paste-extruded sulfonamide compositions
Abstract
Paste-extruded sulfonamide herbicide compositions having
improved spray equipment clean-out properties are made by preparing
a mixture comprising a sulfonamide herbicide free acid, at least
about 50 equivalent % of an inorganic base relative to the
sulfonamide herbicide free acid and sufficient water to form an
extrudable paste, extruding the mixture to form an extrudate, and
drying the extrudate.
Inventors: |
Keenan; JosepheJ; (Townsend,
DE) ; Pugh; LuannM; (Newark, DE) ; Roche;
RobertT; (Newark, DE) |
Correspondence
Address: |
David E Heiser;E. I. Du Pont de Nemours and Company
Legal Patent Records Center
4417 Lancaster Pike
Wilmington
DE
19805
US
|
Family ID: |
31997917 |
Appl. No.: |
10/524807 |
Filed: |
September 9, 2003 |
PCT Filed: |
September 9, 2003 |
PCT NO: |
PCT/US03/28256 |
371 Date: |
February 15, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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60410197 |
Sep 12, 2002 |
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60468706 |
May 7, 2003 |
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Current U.S.
Class: |
504/211 ;
504/212; 504/358 |
Current CPC
Class: |
A01N 25/12 20130101;
A01N 47/36 20130101; A01N 47/36 20130101; A01N 43/90 20130101; A01N
43/90 20130101; A01N 47/36 20130101; A01N 25/14 20130101; A01N
2300/00 20130101; A01N 43/90 20130101; A01N 25/14 20130101; A01N
25/12 20130101; A01N 25/14 20130101; A01N 2300/00 20130101; A01N
25/12 20130101 |
Class at
Publication: |
504/211 ;
504/212; 504/358 |
International
Class: |
A01N 47/36 20060101
A01N047/36; A01N 25/00 20060101 A01N025/00 |
Claims
1. A process for preparing a paste-extruded sulfonamide herbicide
composition comprising (a) preparing a mixture comprising (i) from
2 to 90% by weight on a water-free basis of one or more active
ingredients comprising at least one sulfonamide herbicide free
acid; (ii) from 0 to 95% by weight on a water-free basis of one or
more additives selected from the group consisting of wetting
agents, dispersants, lubricants, anticaking agents, chemical
stabilizers and diluents; and (iii) at least about 50 equivalent %
of base selected from inorganic base equivalents having conjugate
acid pK.sub.as at least 2.1 units greater than the highest pK.sub.a
of the sulfonamide herbicide free acid component; the sum of the
weight percents of all the ingredients in the mixture totaling 100%
on a water-free basis; and (iv) sufficient water to make the
mixture an extrudable paste; (b) extruding the mixture prepared in
(a) through a die or screen to form extrudate; and (c) drying the
extrudate.
2. The process of claim 1 wherein the mixture comprises at least
about 75 equivalent % of base.
3. The process of claim 2 wherein the mixture comprises at least
about 100 equivalent % of base.
4. The process of claim 1 wherein the base comprises an inorganic
base selected from the group consisting of sodium hydrogen
carbonate, sodium carbonate, sodium hydrogen phosphate, sodium
phosphate, potassium hydrogen carbonate, potassium carbonate,
potassium hydrogen phosphate and potassium phosphate.
5. The process of claim 4 wherein the base comprises an inorganic
base selected from the group consisting of sodium carbonate, sodium
phosphate, potassium carbonate and potassium phosphate.
6. The process of claim 5 wherein the base comprises sodium
carbonate.
7. The process of claim 5 wherein the base comprises sodium
phosphate.
8. The process of claim 7 wherein the sodium phosphate is in the
form of the dodecahydrate.
9. The process of claim 1 wherein the mixture comprises from about
0.5 to about 50% by weight of a saccharide on a water-free
basis.
10. The process of claim 1 wherein at least one sulfonamide
herbicide free acid is selected from the group consisting of
amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl,
chlorsulfuron, cinosulfuron, cyclosulfamuron,
ethametsulfuron-methyl, ethoxysulfuron, flupyrsulfuron-methyl,
flazasulfuron, foramsulfuron, halosulfuron-methyl, imazosulfuron,
iodosulfuron-methyl, mesosulfuron-methyl, metsulfuron-methyl,
nicosulfuron, oxasulfuron, primisulfuron-methyl, prosulfuron,
pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl,
sulfosulfuron, thifensulfuron-methyl, triasulfuron,
tribenuron-methyl, trifloxysulfuron, triflusulfuron-methyl,
tritosulfuron, cloransulam-methyl, diclosulam, florasulam,
flumetsulam, metosulam and penoxsulam.
11. The process of claim 10 wherein at least one sulfonamide
herbicide free acid is selected from the group consisting of
azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron,
ethametsulfuron-methyl, flupyrsulfuron-methyl, metsulfuron-methyl,
nicosulfuron, rimsulfuron, sulfometuron-methyl,
thifensulfuron-methyl, tribenuron-methyl and
triflusulfuron-methyl.
12. The process of claim 1 wherein at least one sulfonamide
herbicide free acid is sulfometuron-methyl and the base comprises
sodium phosphate.
13. The process of claim 1 wherein at least one sulfonamide
herbicide free acid is thifensulfuron-methyl and the base comprises
sodium carbonate.
14. The process of claim 1 wherein at least one sulfonamide
herbicide free acid is tribenuron-methyl and the base comprises
sodium carbonate.
15. The process of claim 1 wherein in (a) sufficient water to make
an extrudable paste is added to a solid composition comprising from
2 to 90% by weight on a water-free basis of one or more active
ingredients comprising at least one sulfonamide herbicide free
acid, from 0.5 to 94% by weight on a water-free basis of a
saccharide, from 1 to 20% by weight on a water-free basis of
surfactant component, at least about 50 equivalent % of base
selected from inorganic base equivalents having conjugate acid
pK.sub.as at least 2.1 units greater than the highest pK.sub.a of
the sulfonamide herbicide free acid component, and optionally other
ingredients; the sum of the weight % of all the ingredients in the
solid composition totaling 100% of a water-free basis; and at least
10% of the sulfonamide herbicide content in the solid composition
being in free acid form.
16. The process of claim 1 further comprising a step of sifting the
dried extrudate.
17. A paste-extruded sulfonamide herbicide composition prepared by
the process of claim 1.
Description
BACKGROUND OF THE INVENTION
[0001] Since the discovery of the sulfonamide herbicides comprising
the sulfonylureas and triazolopyrimidines, more than two dozen
sulfonylurea and close to a half dozen triazolopyrimidine
herbicides have been commercially developed for selective weed
control in a wide variety of crops (The Pesticide Manual, Twelfth
Edition, C. D. S. Tomlin, ed., British Crop Protection Council,
Surrey, U.K, 2000). As the mode of action of these sulfonamide
herbicides is inhibition of the enzyme acetolactate synthase (ALS)
found in plants but not animals, sulfonamide herbicides provide a
valued combination of excellent efficacy against weeds with low use
rates and very low toxicity to animals.
[0002] Sulfonamide herbicides like other agricultural chemicals can
be formulated as concentrates in a variety of different forms,
including liquid compositions such as emulsifiable concentrates and
solid compositions such as wettable powders and granules. Granular
compositions can be conveniently transferred and measured like a
liquid, but unlike liquids, very little residue adheres to the
walls of the product container. Furthermore, organic solvents and
vapors are avoided. Compared to wettable powders, granules are
relatively dust-free. A particularly useful type of granules are
those which are water-dispersible. Water-dispersible granules,
sometimes described as "dry flowables", readily disintegrate when
added to water to form a solution or suspension, which can then be
sprayed on the locus to be treated. It is also advantageous for
granular compositions to have good attrition resistance, low
tackiness, and uniform bulk density.
[0003] Water-dispersible granules can be manufactured by a variety
of processes, including fluid-bed granulation, pan granulation,
spray drying, intensive mixing, compaction, paste extrusion and
heat extrusion (such as melt extrusion). The physical dimensions
and porosity of water-dispersible granules depends upon the
manufacturing process used. Fluid bed granulation, spray drying and
intensive mixing give granules that very rapidly break up and
disperse in water because of granule dimensional properties such as
small size, irregular surface and porosity. On the other hand,
paste extrusion and heat extrusion provide granules of relatively
consistent diameter and shape. The consistent diameter of extruded
granules makes them useful in uniform blends as described in U.S.
Pat. No. 6,022,552.
[0004] Granule composition is an important factor for obtaining
sufficiently rapid dispersion of extruded granules. The dispersed
particles formed on dilution should be no larger than 50 microns in
their largest dimension to avoid premature settling, which may
result in uneven application of the pesticide. It is therefore
necessary that all of the components of the formulated product
rapidly and completely disperse or dissolve in the dilution water.
(If all of the components completely dissolve, then they can be
regarded as being dispersed at the molecular level.) Water
dispersibility of granules is determined not only by the
composition of the granules but also by the composition and other
properties of the aqueous medium to which the granules are added.
For example, low temperatures and high concentrations of solutes
can greatly retard granule disintegration.
[0005] Extruded granules are often most conveniently and
cost-effectively prepared through paste extrusion using water to
plasticize a powder mixture, which is then dried after extrusion.
Paste extrusion avoids need for including binders that soften at
elevated temperatures, as is required for heat extrusion. However,
the use in paste extrusion of water as a plasticizer precludes
inclusion of water-activated gas-generating ingredients, which
otherwise can be used for accelerating disintegration and
dispersion of heat-extruded or compacted granules.
[0006] Besides achieving satisfactory granule disintegration and
dispersion, spray equipment clean-out can also be important. As
sulfonamide herbicides comprise a highly active class of
herbicides, it is desirable to clean out spray equipment before the
equipment is subsequently used to treat a crop sensitive to the
sulfonamide herbicide used in the previous application. Clean-out
may require a rinsing procedure that is time-consuming and results
in wastewater requiring proper environmental disposal. Furthermore,
clean-out can be affected if the spray equipment contains organic
deposits remaining from previous crop protection chemical
applications or from other chemicals tank-mixed with the
sulfonamide herbicide composition.
[0007] PCT Patent Application Publication WO 93/16596 describes a
method for reducing residual sulfonylurea herbicide contamination
of spray equipment by requiring as the first step the formulation
of the sulfonylurea active ingredient in the form of an
agriculturally suitable water soluble salt. Although a variety of
methods are known for preparation of salts of sulfonamide
herbicides from the corresponding free acid forms, as processes to
prepare sulfonamide herbicide active ingredient often provide the
free acid form either directly or as part of isolation, conversion
to a salt would require an additional process step. Preferable
would be formulations with improved spray equipment clean-out
properties whereby the free acid form of the sulfonamide herbicide
is directly used in the formulation process.
[0008] Now discovered is a process for conveniently preparing
paste-extruded granular sulfonamide herbicide formulations that not
only have satisfactory water dispersibility but also improved spray
equipment clean-out properties.
SUMMARY OF THE INVENTION
[0009] This invention relates to a process for preparing a
paste-extruded sulfonamide herbicide composition comprising
[0010] (a) preparing a mixture comprising [0011] (i) from 2 to 90%
by weight on a water-free basis of one or more active ingredients
comprising at least one sulfonamide herbicide free acid; [0012]
(ii) from 0 to 95% by weight on a water-free basis of one or more
additives selected from the group consisting of wetting agents,
dispersants, lubricants, anticaking agents, chemical stabilizers
and diluents; and [0013] (iii) at least about 50 equivalent % of
base selected from inorganic base equivalents having conjugate acid
pK.sub.as at least 2.1 units greater than the highest pK.sub.a of
the sulfonamide herbicide free acid component; [0014] the sum of
the weight percents of all the ingredients in the mixture totaling
100% on a water-free basis; and [0015] (iv) sufficient water to
make the mixture an extrudable paste;
[0016] (b) extruding the mixture prepared in (a) through a die or
screen to form extrudate; and
[0017] (c) drying the extrudate.
[0018] The invention also relates to a paste-extruded sulfonamide
herbicide composition prepared by the aforementioned process.
DETAILED DESCRIPTION OF THE INVENTION
[0019] It has been discovered that a paste-extruded sulfonamide
herbicide composition having not only excellent water
dispersibility but significantly improved spray equipment clean-out
properties is obtained from extrusion of a mixture comprising at
least one sulfonamide herbicide free acid by including in the
mixture for extrusion at least about 50 equivalent % of base
selected from inorganic base equivalents having conjugate acid
pK.sub.as at least 2.1 units greater than the pK.sub.a of the
sulfonamide herbicide free acid with the highest pK.sub.a. By
sulfonamide herbicide free acid is meant the free acid form of the
sulfonamide herbicide and not the salt form (wherein the
sulfonamide herbicide is deprotonated at its acidic sulfonamide
center). The mixture for extrusion can also comprise the salt form
of one or more sulfonamide herbicides among the mixture components,
but only the sulfonamide herbicide acid form present is considered
to calculate the at least about 50 equivalent % of base selected
from inorganic base equivalents. Commonly the sulfonamide
herbicides added to prepare the mixture for extrusion are at least
10% in the acid form, typically at least 50%, more typically at
least 80% and most typically at least 90% in the acid form.
[0020] The pK.sub.a values of the sulfonamide herbicides are
determined in water at ambient temperatures, typically about 20 to
25.degree. C. pK.sub.a values can be determined by standard methods
such as the procedure taught below in Analytical Example 1, and
measured values for commercial herbicides are generally published
in such references as The Pesticide Manual, Twelfth Edition edited
by C. D. S. Tomlin (British Crop Protection Council, Surrey, UK,
2000). For the convenience of the reader, Table A below lists
pK.sub.a values for many of the commercially available sulfonamide
herbicides. TABLE-US-00001 TABLE A Molecular Weights and pK.sub.a
Values of Some Sulfonamide Herbicides Sulfonamide Mol. Wt. pK.sub.a
Sulfonylureas amidosulfuron 369.4 3.6 azimsulfuron 424.4 3.6
bensulfuron-methyl 410.4 5.2 chlorimuron-ethyl 414.8 4.2
chlorsulfuron 357.8 3.6 cinosulfuron 413.4 4.7 cyclosulfamuron
421.4 5.0 ethametsulfuron-methyl 410.4 4.6 flazasulfuron 407.3 4.4
flupyrsulfuron-methyl 465.4 4.9 halosulfuron-methyl 434.8 3.4
imazosulfuron 412.8 4.0 iodosulfuron-methyl 507.3 3.2
metsulfuron-methyl 381.4 3.3 nicosulfuron 410.4 4.6 oxasulfuron
406.4 5.1 primisulfuron-methyl 468.3 3.5 prosulfuron 419.4 3.8
pyrazosulfuron-ethyl 414.4 3.7 rimsulfuron 431.4 4.0
sulfometuron-methyl 364.4 5.2 sulfosulfuron 470.5 3.5
thifensulfuron-methyl 387.4 4.0 triasulfuron 401.8 4.6
tribenuron-methyl 395.4 5.0 trifloxysulfuron 437.1 4.8
triflusulfuron-methyl 492.4 4.4 Triazolopyrimidines florasulam
359.3 4.5 metosulam 418.3 4.8 flumetsulam 325.3 4.6 diclosulam
406.2 4.0 cloransulam-methyl 429.8 4.8 penoxsulam 483.4 5.1
[0021] The at least about 50 equivalent % of base in the mixture
for extrusion according to this invention is selected from base
equivalents that are inorganic, i.e. provided by inorganic bases.
Particularly suitable inorganic bases are described in further
detail below. The terms "equivalent % of base" and "base
equivalents" refers to the fact that some inorganic bases can
provide more than one equivalent of basicity per mole. In the
context of the present invention, the number of base equivalents
per mole of base is limited to the base equivalents having
conjugate acid pK.sub.as at least 2.1 units greater that the
highest pK.sub.a of the one or more sulfonamide free acid
components in the mixture. Calculation of number of moles of base
needed to provide at least 50 equivalent % of base is described
further below.
[0022] The pK.sub.a values of conjugate acids of bases can be
determined by standard methods. Published values can be found in a
variety of references, such as The Chemist's Companion by A. J.
Gordon and R. A. Ford (Wiley-Interscience, New York, 1972). For the
convenience of the reader, Table B lists conjugate acid pK.sub.a
values for some common bases. TABLE-US-00002 TABLE B Formula
Weights and Conjugate Acid pK.sub.a Values of Some Bases Base Form.
Wt. First pK.sub.a Second pK.sub.a Third pK.sub.a LiOH 23.95 14.0
-- -- Li.sub.2CO.sub.3 73.89 10.2 6.4 -- Li.sub.3PO.sub.4 115.79
12.7 7.2 2.1 NaOH 40.00 14.0 -- -- NaHCO.sub.3 84.01 6.4 -- --
Na.sub.2CO.sub.3 105.99 10.2 6.4 -- Na.sub.2CO.sub.3.H.sub.2O
124.01 10.2 6.4 -- Na.sub.2HPO.sub.4 141.96 7.2 2.1 --
Na.sub.3PO.sub.4 163.94 12.7 7.2 2.1 Na.sub.3PO.sub.4.12H.sub.2O
380.13 12.7 7.2 2.1 Na.sub.4P.sub.2O.sub.7 265.90 9.0 7.0 2.0 KOH
56.11 14.0 -- -- KHCO.sub.3 100.12 6.4 -- -- K.sub.2CO.sub.3 138.21
10.2 6.4 -- K.sub.2HPO.sub.4 174.18 7.2 2.1 -- K.sub.3PO.sub.4
212.28 12.7 7.2 2.1 K.sub.4P.sub.2O.sub.7 330.35 9.0 7.0 2.0
[0023] The equivalent % of base selected from inorganic base
equivalents is calculated relative to the total number of moles of
the one or more sulfonamide herbicides added to the mixture in
their free acid forms (i.e. not salts), with consideration of the
basicity of the inorganic base equivalents for which conjugate acid
pK.sub.a in water is a least 2.1 units greater Man the pK.sub.a of
the sulfonamide herbicide with highest pK.sub.a. For example, if
one mole of thifensulfuron-methyl and one mole of tribenuron-methyl
in their free acid forms is added to the mixture, the pK.sub.a of
tribenuron-methyl (5.0) is considered instead of the pK.sub.a of
thifensulfuron-methyl (4.0), as the former pK.sub.a is higher. In
this example, the total number of moles of sulfonamide herbicides
in free acid form is two moles, and 50 equivalent % of an inorganic
base would require one equivalent of base. Phosphoric acid contains
three acidic hydrogen atoms, with respective aqueous pK.sub.a of
2.1, 7.2 and 12.7. As only 7.2 and 12.7 are least 2.1 units greater
than 5.0, sodium phosphate is dibasic (i.e. provides two base
equivalents per mole) relative to the requirement that pK.sub.a
difference be at least 2.1 units. Accordingly one equivalent of
base would be provided by one-half mole (i.e. one-half formula
weight amount) of sodium phosphate. Carbonic acid contains two
acidic hydrogen atoms, with respective aqueous pK.sub.a of 6.4 and
10.2. As only 10.2 is at least 2.1 units greater than 5.0, sodium
carbonate is monobasic (i.e. provides one base equivalent per mole)
relative to the requirement that the pK.sub.a difference be at
least 2.1 units. Therefore one mole (i.e. one formula weight
amount) of sodium carbonate would provide one equivalent of
base.
[0024] With many sulfonamide herbicides, particularly those with a
solubility in pH 7 buffered water at ambient temperature (i.e.
about 20 to 30.degree. C.) of greater than about 1000 mg/L,
compositions prepared according to the process of this invention to
include about 50 equivalent % of base relative to the sulfonamide
herbicide free acids will substantially reduce residues in spray
equipment. The addition of base is particularly beneficial for
paste-extruded compositions of sulfonamide herbicides with a
solubility in pH 7 buffered water of less than about 10,000 mg/L,
because for more soluble sulfonamide herbicides spray tank residues
are rarely encountered. (Illustrative examples of sulfonamide
herbicides having a solubility in pH 7 buffered water between 1000
and 10,000 mg/L are chlorimuron-ethyl, metsulfuron-methyl,
thifensulfuron-methyl and tribenuron-methyl.) With sulfonamide
herbicides having a solubility in pH 7 buffered water of less than
about 1000 mg/L, more than 50 equivalent % of base relative to the
sulfonamide herbicide free acids may be needed in the compositions
prepared according to the process of this invention to
significantly reduce residues in spray equipment. (Illustrative
examples of sulfonamide herbicides having a solubility in pH 7
buffered water less than 1000 mg/L are bensulfuron-methyl and
sulfometuron-methyl.) For compositions of these sulfonamide
herbicides, typically about 75 to 100 equivalent % of base
significantly reduces spray residues, and greater amounts (i.e. up
to about 200 equivalent %) of base may be useful in reducing
residues to negligible levels. Solubility of sulfonamide herbicides
in pH 7 buffered water can be determined by standard methods such
as the procedure taught below in Analytical Example 2.
[0025] Therefore to improve spray equipment clean-out properties,
the mixture for extrusion according to the process of this
invention preferably contains at least about 75 equivalent % of
base, and more preferably at least about 100 equivalent % of base
relative to the one or more sulfonamide herbicide free acids.
Furthermore, if the mixture contains acidic substances besides the
sulfonamide herbicide free acids, correspondingly more base should
be added. More than 100 equivalent % of base can be included
relative to the one or more sulfonamide herbicide free acids,
provided that the mixture does not include ingredients unstable to
the base.
[0026] The base in the mixture for extrusion according to the
process of this invention comprises at least one inorganic base.
Inorganic bases particularly suitable for this invention include
those having cations derived from alkali metals or ammonium, and
counterions selected from carbonate, phosphate, oxide, hydroxide
and silicate anions, including dimeric, trimeric and polymeric
forms such as pyrophosphate, tripolyphosphate, polyphosphate,
trisilicate, etc. Illustrative inorganic bases include but are not
limited to sodium phosphate (Na.sub.3PO.sub.4), sodium hydrogen
phosphate (Na.sub.2HPO.sub.4), potassium phosphate
(K.sub.3PO.sub.4), potassium hydrogen phosphate (K.sub.2HPO.sub.4),
ammonium hydrogen phosphate ((NH.sub.4).sub.2HPO.sub.4), sodium
carbonate (Na.sub.2CO.sub.3), sodium hydrogen carbonate
(NaHCO.sub.3), potassium carbonate (K.sub.2CO.sub.3), potassium
hydrogen carbonate (KHCO.sub.3), lithium oxide (Li.sub.2O), lithium
hydroxide (LiOH), lithum carbonate (Li.sub.2CO.sub.3), sodium
hydroxide (NaOH), lithium phosphate (Li.sub.3PO.sub.4), lithium
metasilicate (Li.sub.2SiO.sub.3), lithium orthosilicate
(Li.sub.4SiO.sub.4), potassium hydroxide (KOH), sodium metasilicate
(Na.sub.2SiO.sub.3), sodium orthosilicate (Na.sub.4SiO.sub.4),
potassium pyrophosphate (K.sub.4P.sub.2O.sub.7), sodium
trimetaphosphate ((NaPO.sub.3).sub.3), sodium hexametaphosphate
((NaPO.sub.3).sub.6), sodium polyphosphate (NaPO.sub.3).sub.n),
sodium pyrophosphate (Na.sub.4P.sub.2O.sub.7), sodium
tripolyphosphate (sodium triphosphate, Na.sub.5P.sub.3O.sub.10) and
sodium trisilicate (Na.sub.2Si.sub.3O.sub.7), including their
anhydrous and hydrated forms.
[0027] Preferred for reason of cost, effectiveness and convenience
are inorganic bases containing an alkali metal cation selected from
sodium (Na.sup.+) and potassium (K.sup.+), more preferably sodium.
Also preferred for reason of cost, effectiveness and convenience
are inorganic bases containing a counterion selected from hydrogen
carbonate (HCO.sub.3.sup.-), carbonate (CO.sub.3.sup.2-), hydrogen
phosphate (HPO.sub.4.sup.2-) and phosphate (PO.sub.4.sup.3-), more
preferably carbonate and phosphate. Preferred inorganic bases thus
include sodium hydrogen carbonate, sodium carbonate, sodium
hydrogen phosphate, sodium phosphate, potassium hydrogen carbonate,
potassium carbonate, potassium hydrogen phosphate and potassium
phosphate. These inorganic bases include hydrated forms such as
sodium carbonate monohydrate, sodium hydrogen phosphate
heptahydrate, sodium phosphate dodecahydrate, potassium carbonate
sesquihydrate, potassium hydrogen phosphate trihydrate and
potassium phosphate octahydrate. Inorganic bases more preferred are
sodium carbonate, sodium phosphate, potassium carbonate and
potassium phosphate, including hydrated forms thereof. A most
preferred inorganic base is sodium carbonate, including hydrated
forms thereof. Another most preferred inorganic base is sodium
phosphate, including hydrated forms thereof. While inorganic bases
are useful alone, mixtures of inorganic bases may be
advantageous.
[0028] During the addition of water to prepare an extrudable paste,
the heat of hydration of anhydrous bases can, depending upon amount
and nature of base and the cooling capacity of the mixing or
kneading equipment, cause considerable increase in temperature with
potentially undesirable effect on the chemical constitution and/or
extrudability of the paste. If the temperature increase caused by
anhydrous bases would be excessive, hydrated instead of anhydrous
forms of bases are preferred for preparing the mixture for
extrusion. As the heat of hydration of anhydrous sodium phosphate
is particularly large, the dodecahydrate is a preferred form of
sodium phosphate for the process of this invention.
[0029] Sulfonamide herbicides have as an essential molecular
structure feature a sulfonamide moiety (--S(O).sub.2NH--). As
referred to herein, sulfonamide herbicides particularly comprise
sulfonylurea herbicides wherein the sulfonamide moiety is a
component in a sulfonylurea moiety (--S(O).sub.2NHC(O)NH(R)--) and
triazolopyrimidine herbicides wherein the sulfonyl end of the
sulfonamide moiety is connected to the 2-position of a substituted
[1,2,4]triazolopyrimidine ring system and the amino end of the
sulfonamide moiety is connected to a substituted aryl, typically
phenyl, group. In sulfonylurea herbicides the sulfonyl end of the
sulfonylurea moiety is connected either directly or by way of an
oxygen atom or an optionally substituted amino or methylene group
to a typically substituted cyclic or acyclic group. At the opposite
end of the sulfonylurea bridge, the amino group, which may have a
substituent such as methyl (R being CH.sub.3) instead of hydrogen,
is connected to a heterocyclic group, typically a symmetric
pyrimidine or triazine ring, having one or two substituents such as
methyl, ethyl, trifluoromethyl, methoxy, ethoxy, methylamino,
dimethylamino, ethylamino and the halogens.
[0030] Representative of the sulfonylureas contemplated for use in
this invention are those of the formula: ##STR1## wherein: [0031] J
is selected from the group consisting of ##STR2## ##STR3## [0032] J
is R.sup.13SO.sub.2N(CH.sub.3)--; [0033] R is H or CH.sub.3; [0034]
R.sup.1 is F, Cl, Br, NO.sub.2, C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 haloalkyl, C.sub.3-C.sub.4 cycloalkyl,
C.sub.2-C.sub.4 haloalkenyl, C.sub.1-C.sub.4 alkoxy,
C.sub.1-C.sub.4 haloalkoxy, C.sub.2-C.sub.4 alkoxyalkoxy,
CO.sub.2R.sup.14, C(O)NR.sup.15R.sup.16, SO.sub.2NR.sup.17R.sup.18,
S(O).sub.nR.sup.19, C(O)R.sup.20, CH.sub.2CN or L; [0035] R.sup.2
is H, F, Cl, Br, I, CN, CH.sub.3, OCH.sub.3, SCH.sub.3, CF.sub.3 or
OCF.sub.2H; [0036] R.sup.3 is Cl, NO.sub.2, CO.sub.2CH.sub.3,
CO.sub.2CH.sub.2CH.sub.3, C(O)CH.sub.3, C(O)CH.sub.2CH.sub.3,
C(O)-cyclopropyl, SO.sub.2N(CH.sub.3).sub.2, SO.sub.2CH.sub.3,
SO.sub.2CH.sub.2CH.sub.3, OCH.sub.3 or OCH.sub.2CH.sub.3; [0037]
R.sup.4 is C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.2 haloalkyl
C.sub.1-C.sub.2 alkoxy, C.sub.2-C.sub.4 haloalkenyl, F, Cl, Br,
NO.sub.2, CO.sub.2R.sup.14, C(O)NR.sup.15R.sup.16,
SO.sub.2NR.sup.17R.sup.18, S(O).sub.nR.sup.19, C(O)R.sup.20 or L;
[0038] R.sup.5 is H, F, Cl, Br or CH.sub.3; [0039] R.sup.6 is
C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.2 alkoxy, C.sub.2-C.sub.4
haloalkenyl, F, Cl, Br, CO.sub.2R.sup.14, C(O)NR.sup.15R.sup.16,
SO.sub.2NR.sup.17R.sup.18, S(O).sub.nR.sup.19, C(O)R.sup.20 or L;
[0040] R.sup.7 is H, F, Cl, CH.sub.3 or CF.sub.3; [0041] R.sup.8 is
H, C.sub.1-C.sub.3 alkyl or pyridyl; [0042] R.sup.9 is
C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.2 alkoxy, F, Cl, Br, NO.sub.2,
CO.sub.2R.sup.14, SO.sub.2NR.sup.17R.sup.18, S(O).sub.nR.sup.19,
OCF.sub.2H, C(O)R.sup.20, C.sub.2-C.sub.4 haloalkenyl or L; [0043]
R.sup.10 is H, Cl, F, Br, C.sub.1-C.sub.3 alkyl or C.sub.1-C.sub.2
alkoxy, [0044] R.sup.11 is H, C.sub.1-C.sub.3 alkyl,
C.sub.1-C.sub.2 alkoxy, C.sub.2-C.sub.4 haloalkenyl, F, Cl, Br,
CO.sub.2R.sup.14, C(O)NR.sup.15R.sup.16, SO.sub.2NR.sup.17R.sup.18,
S(O).sub.nR.sup.19, C(O)R.sup.20 or L; [0045] R.sup.12 is halogen,
C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.3 alkylsulfonyl; [0046]
R.sup.13 is C.sub.1-C.sub.4 alkyl; [0047] R.sup.14 is selected from
the group consisting of allyl, propargyl, oxetan-3-yl and
C.sub.1-C.sub.3 alkyl optionally substituted by at least one member
independently selected from halogen, C.sub.1-C.sub.2 alkoxy and CN;
[0048] R.sup.15 is H, C.sub.1-C.sub.3 alkyl or C.sub.1-C.sub.2
alkoxy, [0049] R.sup.16 is C.sub.1-C.sub.2 alkyl; [0050] R.sup.17
is H, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.2 alkoxy, allyl or
cyclopropyl; [0051] R.sup.18 is H or C.sub.1-C.sub.3 alkyl; [0052]
R.sup.19 is C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 haloalkyl, allyl
or propargyl; [0053] R.sup.20 is C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 haloalkyl or C.sub.3-C.sub.5 cycloalkyl optionally
substituted by halogen; [0054] n is 0, 1 or 2; [0055] L is ##STR4##
[0056] L.sup.1 is CH.sub.2, NH or O; [0057] R.sup.21 is selected
from the group H and C.sub.1-C.sub.3 alkyl; [0058] X is selected
from the group H, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy,
C.sub.1-C.sub.4 haloalkoxy, C.sub.1-C.sub.4 haloalkyl,
C.sub.1-C.sub.4 haloalkylthio, C.sub.1-C.sub.4 alkylthio, halogen,
C.sub.2-C.sub.5 alkoxyalkyl, C.sub.2-C.sub.5 alkoxyalkoxy, amino,
C.sub.1-C.sub.3 alkylamino and di(C.sub.1-C.sub.3 alkyl)amino;
[0059] Y is selected from the group H, C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 alkoxy, C.sub.1-C.sub.4 haloalkoxy, C.sub.1-C.sub.4
alkylthio, C.sub.1-C.sub.4 haloalkylthio, C.sub.2-C.sub.5
alkoxyalkyl, C.sub.2-C.sub.5 alkoxyalkoxy, amino, C.sub.1-C.sub.3
alkylamino, di(C.sub.1-C.sub.3 alkyl)amino, C.sub.3C.sub.4
alkenyloxy, C.sub.3-C.sub.4 alkynyloxy, C.sub.2-C.sub.5
alkylthioalkyl, C.sub.2-C.sub.5 alkylsulfinylalkyl, C.sub.2-C.sub.5
alkylsulfonylalkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.2-C.sub.4
alkynyl, C.sub.3-C.sub.5 cycloalkyl, azido and cyano; and [0060] Z
is selected from the group CH and N;
[0061] provided that (i) when one or both of X and Y is C.sub.1
haloalkoxy, then Z is CH; and (ii) when X is halogen, then Z is CH
and Y is OCH.sub.3, OCH.sub.2CH.sub.3, N(OCH.sub.3)CH.sub.3,
NHCH.sub.3, N(CH.sub.3).sub.2 or OCF.sub.2H.
[0062] Representative of the triazolopyrimidines contemplated for
use in this invention are those of the formula: ##STR5## wherein:
[0063] R.sup.22 and R.sup.23 are each independently selected from
halogen, nitro, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl,
C.sub.1-C.sub.4 alkoxy, C.sub.1-C.sub.4 haloalkoxy and
C.sub.2-C.sub.3 alkoxycarbonyl; [0064] R.sup.24 is selected from H,
halogen, C.sub.1-C.sub.4 alkyl and C.sub.1-C.sub.2 alkoxy, [0065]
Y.sup.1 is selected from H, C.sub.1-C.sub.2 alkyl and
C.sub.1-C.sub.2 alkoxy, [0066] Y.sup.2 is selected from H, F, Cl,
Br, C.sub.1-C.sub.2 alkyl and C.sub.1-C.sub.2 alkoxy, [0067]
Y.sup.3 is selected from H, F and methoxy, and [0068] Z.sup.1 is
selected from CH and N; [0069] provided that at least one of
Y.sup.1 and Y.sup.2 is other than H.
[0070] Of note are said triazolopyrimidines wherein Y.sup.3 is H or
F.
[0071] In the above recitations, the term "alkyl", used either
alone or in compound words such as "alkylthio" or "haloalkyl"
includes straight-chain or branched alkyl, such as, methyl, ethyl,
n-propyl, i-propyl, or the different butyl isomers. "Cycloalkyl"
includes, for example, cyclopropyl, cyclobutyl and cyclopentyl.
"Alkenyl" includes straight-chain or branched alkenes such as
ethenyl, 1-propenyl, 2-propenyl, and the different butenyl isomers.
"Alkenyl" also includes polyenes such as 1,2-propadienyl and
2,4-butadienyl. "Alkynyl" includes straight-chain or branched
alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different
butynyl isomers. "Alkynyl" can also include moieties comprised of
multiple triple bonds such as 2,5-hexadiynyl. "Alkoxy" includes,
for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the
different butoxy isomers. "Alkoxyalkyl" denotes alkoxy substitution
on alkyl. Examples of "alkoxyalkyl" include CH.sub.3OCH.sub.2,
CH.sub.3OCH.sub.2CH.sub.2, CH.sub.3CH.sub.2OCH.sub.2,
CH.sub.3CH.sub.2CH.sub.2CH.sub.2OCH.sub.2 and
CH.sub.3CH.sub.2OCH.sub.2CH.sub.2. "Alkoxyalkoxy" denotes alkoxy
substitution on alkoxy. "Alkenyloxy" includes straight-chain or
branched alkenyloxy moieties. Examples of "alkenyloxy" include
H.sub.2C.dbd.CHCH.sub.2O, (CH.sub.3)CH.dbd.CHCH.sub.2O and
CH.sub.2.dbd.CHCH.sub.2CH.sub.2O. "Alkynyloxy" includes
straight-chain or branched alkynyloxy moieties. Examples of
"alkynyloxy" include HC.ident.CCH.sub.2O and
CH.sub.3C.ident.CCH.sub.2O. "Alkylthio" includes branched or
straight-chain alkylthio moieties such as methylthio, ethylthio,
and the different propylthio isomers. "Alkylthioalkyl" denotes
alkylthio substitution on alkyl. Examples of "alkylthioalkyl"
include CH.sub.3SCH.sub.2, CH.sub.3SCH.sub.2CH.sub.2,
CH.sub.3CH.sub.2SCH.sub.2,
CH.sub.3CH.sub.2CH.sub.2CH.sub.2SCH.sub.2 and
CH.sub.3CH.sub.2SCH.sub.2CH.sub.2; "alkylsulfinylalkyl" and
"alkylsulfonylalkyl" include the corresponding sulfoxides and
sulfones, respectively. Other substituents such as "alkylamino",
"dialkylamino" are defined analogously.
[0072] The total number of carbon atoms in a substituent group is
indicated by the "C.sub.i-C.sub.j" prefix where i and j are numbers
from 1 to 5. For example, C.sub.1-C.sub.4 alkyl designates methyl
through butyl, including the various isomers. As further examples,
C.sub.2 alkoxyalkyl designates CH.sub.3OCH.sub.2; C.sub.3
alkoxyalkyl designates, for example, CH.sub.3CH(OCH.sub.3),
CH.sub.3OCH.sub.2CH.sub.2 or CH.sub.3CH.sub.2OCH.sub.2; and C.sub.4
alkoxyalkyl designates the various isomers of an alkyl group
substituted with an alkoxy group containing a total of four carbon
atoms, examples including CH.sub.3CH.sub.2CH.sub.2OCH.sub.2 and
CH.sub.3CH.sub.2OCH.sub.2CH.sub.2.
[0073] The term "halogen", either alone or in compound words such
as "haloalkyl", includes fluorine, chlorine, bromine or iodine.
Further, when used in compound words such as "haloalkyl", said
alkyl may be partially or fully substituted with halogen atoms
which may be the same or different. Examples of "haloalkyl" include
F.sub.3C, ClCH.sub.2, CF.sub.3CH.sub.2 and CF.sub.3CCl.sub.2. The
terms "haloalkoxy", "haloalkylthio", and the like, are defined
analogously to the term "haloalkyl". Examples of "haloalkoxy"
include CF.sub.3O, CCl.sub.3CH.sub.2O, HCF.sub.2CH.sub.2CH.sub.2O
and CF.sub.3CH.sub.2O. Examples of "haloalkylthio" include
CCl.sub.3S, CF.sub.3S, CCl.sub.3CH.sub.2S and
ClCH.sub.2CH.sub.2CH.sub.2S.
[0074] The following sulfonylurea herbicides illustrate the
sulfonylureas useful for this invention: amidosulfuron
(N-[[[[(4,6-dimethoxy-2-pyrimdinyl)amino]carbonyl]amino]-sulfonyl]-N-meth-
ylmethanesulfonamide), azimsulfuron
(N-[[(4,6-dimethoxy-2-pyrimidinyl)-amino]carbonyl]-1-methyl-4-(2-methyl-2-
H-tetrazol-5-yl)-1H-pyrazole-5-sulfonamide), bensulfuron-methyl
(methyl
2-[[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]-sulfonyl]methyl-
]benzoate), chlorimuron-ethyl (ethyl
2-[[[[(4-chloro-6-methoxy-2-pyrimdinyl)amino]carbonyl]amino]sulfonyl]benz-
oate), chlorsulfuron
(2-chloro-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benze-
nesulfonamide), cinosulfuron
(N-[[(4,6-dimethoxy-1,3,5-triazin-2-yl)amino]carbonyl]-2-(2-methoxyethoxy-
)benzenesulfonamide), cyclosulfamuron
(N-[[[2-(cyclopropylcarbonyl)phenyl]amino]sulfonyl]-N.sup.1-(4,6-dimethox-
ypyrimidin-2-yl)urea), ethametsulfuron-methyl (methyl
2-[[[[[4-ethoxy-6-(methylamino)-1,3,5-triazin-2-yl]amino]carbonyl]amino]s-
ulfonyl]benzoate), ethoxysulfuron (2-ethoxyphenyl
[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]sulfamate),
flupyrsulfuron-methyl (methyl
2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-amino]sulfonyl]-6-(tri-
fluoromethyl)-3-pyridinecarboxylate), flazasulfuron
(N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-3-(trifluoromethyl)-2-p-
yridinesulfonamide), foramsulfuron
(2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl](formyl-
amino)-N,N-dimethylbenzamide), halosulfuron-methyl (methyl
3-chloro-5-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl-
]-1-methyl-1H-pyrazole-4-carboxylate), imazosulfuron
(2-chloro-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-imidazo[1,2-a]-
pyridine-3-sulfonamide), iodosulfuron-methyl (methyl
4-iodo-2-[[[[(4-methoxy-6-methyl
1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate),
mesosulfuron-methyl (methyl
2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-4-[[(me-
thylsulfonyl)amino]methyl]benzoate), metsulfuron-methyl (methyl
2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfony-
l]-benzoate), nicosulfuron
(2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]-sulfonyl]-N,N-d-
imethyl-3-pyridinecarboxamide), oxasulfuron (3-oxetanyl
2-[[[[(4,6-dimethyl-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate)-
, primisulfuron-methyl (methyl
2-[[[[[4,6-bis(trifluoromethoxy)-2-pyrimidinyl]amino]carbonyl]amino]sulfo-
nyl]-benzoate), prosulfuron
(N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]-2-(3,3,3-trif-
luoropropyl)benzenesulfonamide), pyrazosulfuron-ethyl (ethyl
5-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-1-methy-
l-1H-pyrazole-4-carboxylate), rimsulfuron
(N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-3-(ethylsulfonyl)-2-pyr-
idinesulfonamide), sulfometuron-methyl (methyl
2-[[[[(4,6-dimethyl-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate)-
, sulfosulfuron
(N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-2-(ethylsulfonyl)imidaz-
o[1,2-.alpha.]pyridine-3-sulfonamide), thifensulfuron-methyl
(methyl
3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]-carbonyl]amino]sulfon-
yl]-2-thiophenecarboxylate), triasulfuron
(2-(2-chloroethoxy)-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carb-
onyl]benzenesulfonamide), tribenuron-methyl (methyl
2-[[[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino]carbonyl]-a-
mino]sulfonyl]benzoate), trifloxysulfuron
(N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]-carbonyl]-3-(2,2,2-trifluoroetho-
xy)-2-pyridinesulfonamide), triflusulfuron-methyl (methyl
2-[[[[[4-dimethylamino)-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]amin-
o]carbonyl]amino]-sulfonyl]-3-methylbenzoate) and tritosulfuron
(N-[[[4-methoxy-6-(trifluoromethyl)-1,3,5-triazin-2-yl]amino]carbonyl]-2--
(trifluoromethyl)benzenesulfonamide).
[0075] The following sulfonylureas are preferred for use in the
disclosed invention: azinmsulfuron, bensulfuron-methyl,
chlorimuron-ethyl, chlorsulfuron, ethametsulfuron-methyl,
flupyrsulfuron-methyl, metsulfuron-methyl, nicosulfuron,
rimsulfuron, sulfometuron-methyl, thifensulfuron-methyl,
tribenuron-methyl and triflusulfuron-methyl.
[0076] The following triazolopyrimidine herbicides illustrate the
triazolopyrimidines useful for this invention: cloransulam-methyl
(methyl
3-chloro-2-[[(5-ethoxy-7-fluoro[1,2,4]-triazolo[1,5-c]pyrimidin-2-yl)sulf-
onyl]amino]benzoate, diclosulam
(N-(2,6-dichlorophenyl)-5-ethoxy-7-fluoro[1,2,4]triazolo[1,5-c]pyrimidine-
-2-sulfonamide, florasulam
(N-(2,6-difluorophenyl)-8-fluoro-5-methoxy[1,2,4]triazolo[1,5-c]pyrimidin-
e-2-sulfonamide), flumetsulam
(N-(2,6-difluorophenyl)-5-methyl[1,2,4]triazolo[1,5-.alpha.]pyrimidine-2--
sulfonamide), metosulam
(N-(2,6-dichloro-3-methylphenyl)-5,7-dimethoxy[1,2,4]triazolo-[1,5-a]pyri-
midine-2-sulfonamide) and penoxsulam
(2-(2,2-difluoroethoxy)-N-(5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidin-2-
-yl)-6-(trifluoromethyl)benzenesulfonamide).
[0077] Of note for the process of this invention are sulfonamide
herbicides selected from the group consisting of amidosulfuron,
azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron,
cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl,
ethoxysulfuron, flupyrsulfuron-methyl, flazasulfuron,
foramsulfuron, halosulfuron-methyl, imazosulfuron,
iodosulfuron-methyl, mesosulfuron-methyl, metsulfuron-methyl,
nicosulfuron, oxasulfuron, primisulfuron-methyl, prosulfuron,
pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl,
sulfosulfuron, thifensulfuron-methyl, triasulfuron,
tribenuron-methyl, trifloxysulfuron, triflusulfuron-methyl,
tritosulfuron, cloransulam-methyl, diclosulam, florasulam,
flumetsulam and metosulam.
[0078] Preferred embodiments include: [0079] Preferred 1. The
process of the invention wherein the mixture comprises
amidosulfuron. [0080] Preferred 1A. The process of Preferred 1
wherein the mixture comprises at least about 75 equivalent % of
inorganic base relative to amidosulfuron. [0081] Preferred 1B. The
process of Preferred 1 wherein the mixture comprises at least about
100 equivalent % of inorganic base relative to amidosulfuron.
[0082] Preferred 1C. The process of Preferred 1, 1A or 1B wherein
the inorganic base comprises at least one base selected from sodium
carbonate, sodium hydrogen carbonate, sodium phosphate, sodium
hydrogen phosphate, potassium carbonate, potassium hydrogen
carbonate, potassium phosphate and potassium hydrogen phosphate,
including the hydrated forms thereof. [0083] Preferred 2. The
process of the invention wherein the mixture comprises
azimsulfuron. [0084] Preferred 2A. The process of Preferred 2
wherein the mixture comprises at least about 75 equivalent % of
inorganic base relative to azimsulfuron. [0085] Preferred 2B. The
process of Preferred 2 wherein the mixture comprises at least about
100 equivalent % of inorganic base relative to azimsulfuron. [0086]
Preferred 2C. The process of Preferred 2, 2A or 2B wherein the
inorganic base comprises at least one base selected from sodium
carbonate, sodium hydrogen carbonate, sodium phosphate, sodium
hydrogen phosphate, potassium carbonate, potassium hydrogen
carbonate, potassium phosphate and potassium hydrogen phosphate,
including the hydrated forms thereof. [0087] Preferred 3. The
process of the invention wherein the mixture comprises
bensulfuron-methyl. [0088] Preferred 3A. The process of Preferred 3
wherein the mixture comprises at least about 100 equivalent % of
inorganic base relative to bensulfuron-methyl. [0089] Preferred 3B.
The process of Preferred 3 or 3A wherein the inorganic base
comprises at least one base selected from sodium carbonate, sodium
phosphate, potassium carbonate and potassium phosphate, including
the hydrated forms thereof. [0090] Preferred 4. The process of the
invention wherein the mixture comprises chlorimuron-ethyl [0091]
Preferred 4A. The process of Preferred 4 wherein the mixture
comprises at least about 75 equivalent % of inorganic base relative
to chlorimuron-ethyl. [0092] Preferred 4B. The process of Preferred
4 or 4A wherein the inorganic base comprises at least one base
selected from sodium carbonate, sodium hydrogen carbonate, sodium
phosphate, sodium hydrogen phosphate, potassium carbonate,
potassium hydrogen carbonate, potassium phosphate and potassium
hydrogen phosphate, including the hydrated forms thereof. [0093]
Preferred 5. The process of the invention wherein the mixture
comprises chlorsulfuron. [0094] Preferred 5A. The process of
Preferred 5 wherein the mixture comprises at least about 75
equivalent % of inorganic base relative to chlorsulfuron. [0095]
Preferred 5B. The process of Preferred 5 wherein the mixture
comprises at least about 100 equivalent % of inorganic base
relative to chlorsulfuron. [0096] Preferred 5C. The process of
Preferred 5, 5A or 5B wherein the inorganic base comprises at least
one base selected from sodium carbonate, sodium hydrogen carbonate,
sodium phosphate, sodium hydrogen phosphate, potassium carbonate,
potassium hydrogen carbonate, potassium phosphate and potassium
hydrogen phosphate, including the hydrated forms thereof. [0097]
Preferred 6. The process of the invention wherein the mixture
comprises cinosulfuron. [0098] Preferred 6A. The process of
Preferred 6 wherein the mixture comprises at least about 75
equivalent % of inorganic base relative to cinosulfuron. [0099]
Preferred 6B. The process of Preferred 6 wherein the mixture
comprises at least about 100 equivalent % of inorganic base
relative to cinosulfuron. [0100] Preferred 6C. The process of
Preferred 6, 6A or 6B wherein the inorganic base comprises at least
one base selected from sodium carbonate, sodium phosphate, sodium
hydrogen phosphate, potassium carbonate, potassium phosphate and
potassium hydrogen phosphate, including the hydrated forms thereof.
[0101] Preferred 7. The process of the invention wherein the
mixture comprises cyclosulfamuron. [0102] Preferred 7A. The process
of Preferred 7 wherein the mixture comprises at least about 75
equivalent % of inorganic base relative to cyclosulfamuron. [0103]
Preferred 7B. The process of Preferred 7 wherein the mixture
comprises at least about 100 equivalent % of inorganic base
relative to cyclosulfamuron. [0104] Preferred 7C. The process of
Preferred 7, 7A or 7B wherein the inorganic base comprises at least
one base selected from sodium carbonate, sodium phosphate, sodium
hydrogen phosphate, potassium carbonate, potassium phosphate and
potassium hydrogen phosphate, including the hydrated forms thereof.
[0105] Preferred 8. The process of the invention wherein the
mixture comprises ethametsulfuron-methyl. [0106] Preferred 8A. The
process of Preferred 8 wherein the mixture comprises at least about
75 equivalent % of inorganic base relative to
ethametsulfuron-methyl. [0107] Preferred 8B. The process of
Preferred 8 wherein the mixture comprises at least about 100
equivalent % of inorganic base relative to ethametsulfuron-methyl.
[0108] Preferred 8C. The process of Preferred 8, 8A or 8B wherein
the inorganic base comprises at least one base selected from sodium
carbonate, sodium phosphate, sodium hydrogen phosphate, potassium
carbonate, potassium phosphate and potassium hydrogen phosphate,
including the hydrated forms thereof. [0109] Preferred 9. The
process of the invention wherein the mixture comprises
ethoxysulfuron. [0110] Preferred 9A. The process of Preferred 9
wherein the mixture comprises at least about 75 equivalent % of
inorganic base relative to ethoxysulfuron. [0111] Preferred 9B. The
process of Preferred 9 wherein the mixture comprises at least about
100 equivalent % of inorganic base relative to ethoxysulfuron.
[0112] Preferred 9C. The process of Preferred 9, 9A or 9B wherein
the inorganic base comprises at least one base selected from sodium
carbonate, sodium phosphate, sodium hydrogen phosphate, potassium
carbonate, potassium phosphate and potassium hydrogen phosphate,
including the hydrated forms thereof. [0113] Preferred 10. The
process of the invention wherein the mixture comprises
flupyrsulfuron-methyl. [0114] Preferred 10A. The process of
Preferred 10 wherein the mixture comprises at least about 75
equivalent % of inorganic base relative to flupyrsulfuron-methyl.
[0115] Preferred 10B. The process of Preferred 10 wherein the
mixture comprises at least about 100 equivalent % of inorganic base
relative to flupyrsulfuron-methyl. [0116] Preferred 10C. The
process of Preferred 10, 10A or 10B wherein the inorganic base
comprises at least one base selected from sodium carbonate, sodium
phosphate, sodium hydrogen phosphate, potassium carbonate,
potassium phosphate and potassium hydrogen phosphate, including the
hydrated forms thereof. [0117] Preferred 11. The process of the
invention wherein the mixture comprises flazasulfuron. [0118]
Preferred 11A. The process of Preferred 11 wherein the mixture
comprises at least about 75 equivalent % of inorganic base relative
to flazasulfuron. [0119] Preferred 11B. The process of Preferred 11
wherein the mixture comprises at least about 100 equivalent % of
inorganic base relative to flazasulfuron. [0120] Preferred 11C. The
process of Preferred 11, 11A or 11B wherein the inorganic base
comprises at least one base selected from sodium carbonate, sodium
phosphate, sodium hydrogen phosphate, potassium carbonate,
potassium phosphate and potassium hydrogen phosphate, including the
hydrated forms thereof. [0121] Preferred 12. The process of the
invention wherein the mixture comprises foramsulfuron. [0122]
Preferred 12A. The process of Preferred 12 wherein the mixture
comprises at least about 75 equivalent % of inorganic base relative
to foramsulfuron. [0123] Preferred 12B. The process of Preferred 12
wherein the mixture comprises at least about 100 equivalent % of
inorganic base relative to foramsulfuron. [0124] Preferred 12C. The
process of Preferred 12, 12A or 12B wherein the inorganic base
comprises at least one base selected from sodium carbonate, sodium
phosphate, sodium hydrogen phosphate, potassium carbonate,
potassium phosphate and potassium hydrogen phosphate, including the
hydrated forms thereof. [0125] Preferred 13. The process of the
invention wherein the mixture comprises halosulfuron-methyl. [0126]
Preferred 13A. The process of Preferred 13 wherein the mixture
comprises at least about 75 equivalent % of inorganic base relative
to halosulfuron-methyl. [0127] Preferred 13B. The process of
Preferred 13 wherein the mixture comprises at least about 100
equivalent % of inorganic base relative to halosulfuron-methyl.
[0128] Preferred 13C. The process of Preferred 13, 13A or 13B
wherein the inorganic base comprises at least one base selected
from sodium carbonate, sodium hydrogen carbonate, sodium phosphate,
sodium hydrogen phosphate, potassium carbonate, potassium hydrogen
carbonate, potassium phosphate and potassium hydrogen phosphate,
including the hydrated forms thereof. [0129] Preferred 14. The
process of the invention wherein the mixture comprises
imazosulfuron. [0130] Preferred 14A. The process of Preferred 14
wherein the mixture comprises at least about 75 equivalent % of
inorganic base relative to imazosulfuron. [0131] Preferred 14B. The
process of Preferred 14 wherein the mixture comprises at least
about 100 equivalent % of inorganic base relative to imazosulfuron.
[0132] Preferred 14C. The process of Preferred 14, 14A or 14B
wherein the inorganic base comprises at least one base selected
from sodium carbonate, sodium hydrogen carbonate, sodium phosphate,
sodium hydrogen phosphate, potassium carbonate, potassium hydrogen
carbonate, potassium phosphate and potassium hydrogen phosphate,
including the hydrated forms thereof. [0133] Preferred 15. The
process of the invention wherein the mixture comprises
iodosulfuron-methyl. [0134] Preferred 15A. The process of Preferred
15 wherein the mixture comprises at least about 75 equivalent % of
inorganic base relative to iodosulfuron-methyl. [0135] Preferred
15B. The process of Preferred 15 wherein the mixture comprises at
least about 100 equivalent % of inorganic base relative to
iodosulfuron-methyl. [0136] Preferred 15C. The process of Preferred
15, 15A or 15B wherein the inorganic base comprises at least one
base selected from sodium carbonate, sodium hydrogen carbonate,
sodium phosphate, sodium hydrogen phosphate, potassium carbonate,
potassium hydrogen carbonate, potassium phosphate and potassium
hydrogen phosphate, including the hydrated forms thereof. [0137]
Preferred 16. The process of the invention wherein the mixture
comprises mesosulfuron-methyl. [0138] Preferred 16A. The process of
Preferred 16 wherein the mixture comprises at least about 75
equivalent % of inorganic base relative to mesosulfuron-methyl.
[0139] Preferred 16B. The process of Preferred 16 wherein the
mixture comprises at least about 100 equivalent % of inorganic base
relative to mesosulfuron-methyl. [0140] Preferred 16C. The process
of Preferred 16, 16A or 16B wherein the inorganic base comprises at
least one base selected from sodium carbonate, sodium phosphate,
sodium hydrogen phosphate, potassium carbonate, potassium phosphate
and potassium hydrogen phosphate, including the hydrated forms
thereof. [0141] Preferred 17. The process of the invention wherein
the mixture comprises metsulfuron-methyl. [0142] Preferred 17A. The
process of Preferred 17 wherein the mixture comprises at least
about 75 equivalent % of inorganic base relative to
metsulfuron-methyl. [0143] Preferred 17B. The process of Preferred
17 wherein the mixture comprises at least about 100 equivalent % of
inorganic base relative to metsulfuron-methyl. [0144] Preferred
17C. The process of Preferred 17, 17A or 17B wherein the inorganic
base comprises at least one base selected from sodium carbonate,
sodium hydrogen carbonate, sodium phosphate, sodium hydrogen
phosphate, potassium carbonate, potassium hydrogen carbonate,
potassium phosphate and potassium hydrogen phosphate, including the
hydrated forms thereof. [0145] Preferred 18. The process of the
invention wherein the mixture comprises nicosulfuron. [0146]
Preferred 18A. The process of Preferred 18 wherein the mixture
comprises at least about 75 equivalent % of inorganic base relative
to nicosulfuron. [0147] Preferred 18B. The process of Preferred 18
wherein the mixture comprises at least about 100 equivalent % of
inorganic base relative to nicosulfuron. [0148] Preferred 18C. The
process of Preferred 18, 18A or 18B wherein the inorganic base
comprises at least one base selected from sodium carbonate, sodium
phosphate, sodium hydrogen phosphate, potassium carbonate,
potassium phosphate and potassium hydrogen phosphate, including the
hydrated forms thereof. [0149] Preferred 19. The process of the
invention wherein the mixture comprises oxasulfuron. [0150]
Preferred 19A. The process of Preferred 19 wherein the mixture
comprises at least about 75 equivalent % of inorganic base relative
to oxasulfuron. [0151] Preferred 19B. The process of Preferred 19
wherein the mixture comprises at least about 100 equivalent % of
inorganic base relative to oxasulfuron. [0152] Preferred 19C. The
process of Preferred 19, 19A or 19B wherein the inorganic base
comprises at least one base selected from sodium carbonate, sodium
phosphate, sodium hydrogen phosphate, potassium carbonate,
potassium phosphate and potassium hydrogen phosphate, including the
hydrated forms thereof. [0153] Preferred 20. The process of the
invention wherein the mixture comprises primisulfuron-methyl.
[0154] Preferred 20A. The process of Preferred 20 wherein the
mixture comprises at least about 75 equivalent % of inorganic base
relative to primisulfuron-methyl. [0155] Preferred 20B. The process
of Preferred 20 wherein the mixture comprises at least about 100
equivalent % of inorganic base relative to primisulfuron-methyl.
[0156] Preferred 20C. The process of Preferred 20, 20A or 20B
wherein the inorganic base comprises at least one base selected
from sodium carbonate, sodium hydrogen carbonate, sodium phosphate,
sodium hydrogen phosphate, potassium carbonate, potassium hydrogen
carbonate, potassium phosphate and potassium hydrogen phosphate,
including the hydrated forms thereof. [0157] Preferred 21. The
process of the invention wherein the mixture comprises prosulfuron.
[0158] Preferred 21A. The process of Preferred 21 wherein the
mixture comprises at least about 75 equivalent % of inorganic base
relative to prosulfuron. [0159] Preferred 21B. The process of
Preferred 21 wherein the mixture comprises at least about 100
equivalent % of inorganic base relative to prosulfuron.
[0160] Preferred 21C. The process of Preferred 21, 21A or 21B
wherein the inorganic base comprises at least one base selected
from sodium carbonate, sodium hydrogen carbonate, sodium phosphate,
sodium hydrogen phosphate, potassium carbonate, potassium hydrogen
carbonate, potassium phosphate and potassium hydrogen phosphate,
including the hydrated forms thereof. [0161] Preferred 22. The
process of the invention wherein the mixture comprises
pyrazosulfuron-ethyl. [0162] Preferred 22A. The process of
Preferred 22 wherein the mixture comprises at least about 75
equivalent % of inorganic base relative to pyrazosulfuron-ethyl.
[0163] Preferred 22B. The process of Preferred 22 wherein the
mixture comprises at least about 100 equivalent % of inorganic base
relative to pyrazosulfuron-ethyl. [0164] Preferred 22C. The process
of Preferred 22, 22A or 22B wherein the inorganic base comprises at
least one base selected from sodium carbonate, sodium hydrogen
carbonate, sodium phosphate, sodium hydrogen phosphate, potassium
carbonate, potassium hydrogen carbonate, potassium phosphate and
potassium hydrogen phosphate, including the hydrated forms thereof.
[0165] Preferred 23. The process of the invention wherein the
mixture comprises rimsulfuron. [0166] Preferred 23A. The process of
Preferred 23 wherein the mixture comprises at least about 75
equivalent % of inorganic base relative to rimsulfuron. [0167]
Preferred 23B. The process of Preferred 23 wherein the mixture
comprises at least about 100 equivalent % of inorganic base
relative to rimsulfuron. [0168] Preferred 23C. The process of
Preferred 23, 23A or 23B wherein the inorganic base comprises at
least one base selected from sodium carbonate, sodium hydrogen
carbonate, sodium phosphate, sodium hydrogen phosphate, potassium
carbonate, potassium hydrogen carbonate, potassium phosphate and
potassium hydrogen phosphate, including the hydrated forms thereof.
[0169] Preferred 24. The process of the invention wherein the
mixture comprises sulfometuron-methyl. [0170] Preferred 24A. The
process of Preferred 24 wherein the mixture comprises at least
about 100 equivalent % of inorganic base relative to
sulfometuron-methyl. [0171] Preferred 24B. The process of Preferred
24 or 24A wherein the inorganic base comprises at least one base
selected from sodium carbonate, sodium phosphate, potassium
carbonate and potassium phosphate, including the hydrated forms
thereof. [0172] Preferred 25. The process of the invention wherein
the mixture comprises sulfosulfuron. [0173] Preferred 25A. The
process of Preferred 25 wherein the mixture comprises at least
about 75 equivalent % of inorganic base relative to sulfosulfuron.
[0174] Preferred 25B. The process of Preferred 25 wherein the
mixture comprises at least about 100 equivalent % of inorganic base
relative to sulfosulfuron. [0175] Preferred 25C. The process of
Preferred 25, 25A or 25B wherein the inorganic base comprises at
least one base selected from sodium carbonate, sodium hydrogen
carbonate, sodium phosphate, sodium hydrogen phosphate, potassium
carbonate, potassium hydrogen carbonate, potassium phosphate and
potassium hydrogen phosphate, including the hydrated forms thereof.
[0176] Preferred 26. The process of the invention wherein the
mixture comprises thifensulfuron-methyl. [0177] Preferred 26A. The
process of Preferred 26 wherein the mixture comprises at least
about 75 equivalent % of inorganic base relative to
thifensulfuron-methyl. [0178] Preferred 26B. The process of
Preferred 26 wherein the mixture comprises at least about 100
equivalent % of inorganic base relative to thifensulfuron-methyl.
[0179] Preferred 26C. The process of Preferred 26, 26A or 26B
wherein the inorganic base comprises at least one base selected
from sodium carbonate, sodium hydrogen carbonate, sodium phosphate,
sodium hydrogen phosphate, potassium carbonate, potassium hydrogen
carbonate, potassium phosphate and potassium hydrogen phosphate,
including the hydrated forms thereof. [0180] Preferred 27. The
process of the invention wherein the mixture comprises
tribenuron-methyl. [0181] Preferred 27A. The process of Preferred
27 wherein the mixture comprises at least about 75 equivalent % of
inorganic base relative to tribenuron-methyl. [0182] Preferred 27B.
The process of Preferred 27 wherein the mixture comprises at least
about 100 equivalent % of inorganic base relative to
tribenuron-methyl. [0183] Preferred 27C. The process of Preferred
27, 27A or 27B wherein the inorganic base comprises at least one
base selected from sodium carbonate, sodium phosphate, sodium
hydrogen phosphate, potassium carbonate, potassium phosphate and
potassium hydrogen phosphate, including the hydrated forms thereof.
[0184] Preferred 28. The process of the invention wherein the
mixture comprises trifloxysulfuron. [0185] Preferred 28A. The
process of Preferred 28 wherein the mixture comprises at least
about 75 equivalent % of inorganic base relative to
trifloxysulfuron. [0186] Preferred 28B. The process of Preferred 28
wherein the mixture comprises at least about 100 equivalent % of
inorganic base relative to trifloxysulfuron. [0187] Preferred 28C.
The process of Preferred 28, 28A or 28B wherein the inorganic base
comprises at least one base selected from sodium carbonate, sodium
phosphate, sodium hydrogen phosphate, potassium carbonate,
potassium phosphate and potassium hydrogen phosphate, including the
hydrated forms thereof. [0188] Preferred 29. The process of the
invention wherein the mixture comprises triflusulfuron-methyl.
[0189] Preferred 29A. The process of Preferred 29 wherein the
mixture comprises at least about 75 equivalent % of inorganic base
relative to triflusulfuron-methyl. [0190] Preferred 29B. The
process of Preferred 29 wherein the mixture comprises at least
about 100 equivalent % of inorganic base relative to
triflusulfuron-methyl. [0191] Preferred 29C. The process of
Preferred 29, 29A or 29B wherein the inorganic base comprises at
least one base selected from sodium carbonate, sodium phosphate,
sodium hydrogen phosphate, potassium carbonate, potassium phosphate
and potassium hydrogen phosphate, including the hydrated forms
thereof. [0192] Preferred 30. The process of the invention wherein
the mixture comprises tritosulfuron. [0193] Preferred 30A. The
process of Preferred 30 wherein the mixture comprises at least
about 75 equivalent % of inorganic base relative to tritosulfuron.
[0194] Preferred 30B. The process of Preferred 30 wherein the
mixture comprises at least about 100 equivalent % of inorganic base
relative to tritosulfuron. [0195] Preferred 30C. The process of
Preferred 30, 30A or 30B wherein the inorganic base comprises at
least one base selected from sodium carbonate, sodium hydrogen
carbonate, sodium phosphate, sodium hydrogen phosphate, potassium
carbonate, potassium hydrogen carbonate, potassium phosphate and
potassium hydrogen phosphate, including the hydrated forms thereof.
[0196] Preferred 31. The process of the invention wherein the
mixture comprises cloransulam-methyl. [0197] Preferred 31A. The
process of Preferred 31 wherein the mixture comprises at least
about 75 equivalent % of inorganic base relative to
cloransulam-methyl. [0198] Preferred 31B. The process of Preferred
31 wherein the mixture comprises at least about 100 equivalent % of
inorganic base relative to cloransulam-methyl. [0199] Preferred
31C. The process of Preferred 31, 31A or 31B wherein the inorganic
base comprises at least one base selected from sodium carbonate,
sodium phosphate, sodium hydrogen phosphate, potassium carbonate,
potassium phosphate and potassium hydrogen phosphate, including the
hydrated forms thereof. [0200] Preferred 32. The process of the
invention wherein the mixture comprises diclosulam. [0201]
Preferred 32A. The process of Preferred 32 wherein the mixture
comprises at least about 75 equivalent % of inorganic base relative
to diclosulam. [0202] Preferred 32B. The process of Preferred 32
wherein the mixture comprises at least about 100 equivalent % of
inorganic base relative to diclosulam. [0203] Preferred 32C. The
process of Preferred 32, 32A or 32B wherein the inorganic base
comprises at least one base selected from sodium carbonate, sodium
hydrogen carbonate, sodium phosphate, sodium hydrogen phosphate,
potassium carbonate, potassium hydrogen carbonate, potassium
phosphate and potassium hydrogen phosphate, including the hydrated
forms thereof. [0204] Preferred 33. The process of the invention
wherein the mixture comprises florasulam. [0205] Preferred 33A. The
process of Preferred 33 wherein the mixture comprises at least
about 75 equivalent % of inorganic base relative to florasulam.
[0206] Preferred 33B. The process of Preferred 33 wherein the
mixture comprises at least about 100 equivalent % of inorganic base
relative to florasulam. [0207] Preferred 33C. The process of
Preferred 33, 33A or 33B wherein the inorganic base comprises at
least one base selected from sodium carbonate, sodium phosphate,
sodium hydrogen phosphate, potassium carbonate, potassium phosphate
and potassium hydrogen phosphate, including the hydrated forms
thereof. [0208] Preferred 34. The process of the invention wherein
the mixture comprises flumetsulam. [0209] Preferred 34A. The
process of Preferred 34 wherein the mixture comprises at least
about 75 equivalent % of inorganic base relative to flumetsulam.
[0210] Preferred 34B. The process of Preferred 34 wherein the
mixture comprises at least about 100 equivalent % of inorganic base
relative to flumetsulam. [0211] Preferred 34C. The process of
Preferred 34, 34A or 34B wherein the inorganic base comprises at
least one base selected from sodium carbonate, sodium phosphate,
sodium hydrogen phosphate, potassium carbonate, potassium phosphate
and potassium hydrogen phosphate, including the hydrated forms
thereof. [0212] Preferred 35. The process of the invention wherein
the mixture comprises metosulam. [0213] Preferred 35A. The process
of Preferred 35 wherein the mixture comprises at least about 75
equivalent % of inorganic base relative to metosulam. [0214]
Preferred 35B. The process of Preferred 35 wherein the mixture
comprises at least about 100 equivalent % of inorganic base
relative to metosulam. [0215] Preferred 35C. The process of
Preferred 35, 35A or 35B wherein the inorganic base comprises at
least one base selected from sodium carbonate, sodium phosphate,
sodium hydrogen phosphate, potassium carbonate, potassium phosphate
and potassium hydrogen phosphate, including the hydrated forms
thereof. [0216] Preferred 36. The process of the invention wherein
the mixture comprises penoxsulam. [0217] Preferred 36A. The process
of Preferred 36 wherein the mixture comprises at least about 75
equivalent % of inorganic base relative to penoxsulam. [0218]
Preferred 36B. The process of Preferred 36 wherein the mixture
comprises at least about 100 equivalent % of inorganic base
relative to penoxsulam. [0219] Preferred 36C. The process of
Preferred 36, 36A or 36B wherein the inorganic base comprises at
least one base selected from sodium carbonate, sodium phosphate,
sodium hydrogen phosphate, potassium carbonate, potassium phosphate
and potassium hydrogen phosphate, including the hydrated forms
thereof.
[0220] Preferred compositions include those prepared by the
preferred processes of the invention.
[0221] The mixture for extrusion according the process of this
invention and the water-dispersible granular composition prepared
therefrom may include other active ingredients besides sulfonamide
herbicides. These other active ingredients may include herbicides,
plant growth regulants, herbicide safeners, insecticides, insect
antifeedants, miticides, nematocides, bactericides and fungicides.
Most commonly, the other active ingredients will be herbicides or
herbicide safeners. Examples of herbicides include acetochlor,
acifluorfen, aclonifen, alachlor, alloxydim, ametryn, amicarbazone,
amitrole, anilofos, asulam, atrazine, azafenidin, beflubutamid,
benazolin, benfluralin, benfuresate, bensulide, bentazone,
benzobicyclon, benzofenap, bifenox, bilanafos, bispyribac,
bromacil, bromobutide, bromoxynil, butachlor, butafenacil,
butamifos, butralin, butroxydim, butylate, cafenstrole,
carbetamide, carfentrazone-ethyl, chloramben, chlorbromuron,
chlorflurenol-methyl, chloridazon, chlorotoluron, chlorpropham,
chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin,
clethodim, clodinafop-propargyl, clomazone, clomeprop, clopyralid,
cumyluron, cyanazine, cycloate, cycloxydim, cyhalofop-butyl, 2,4-D,
daimuron, 2,4-DB, dazomet, desmedipham, dicamba, dichlobenil,
dichlorprop, diclofop-methyl, difenzoquat metilsulfate,
diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor,
dimethametryn, dimethenamid, dimethipin, dinitramine, dinoterb,
diphenamid, diquat dibromide, dithiopyr, diuron, endothal, EPTC,
esprocarb, ethalfluralin, ethofumesate, etobenzanid,
fenoxaprop-P-ethyl, fentrazamide, fenuron, flamprop-M,
fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone,
fluchloralin, flufenacet, flumichlorac-pentyl, flumioxazin,
fluometuron, fluoroglycofen-ethyl, fluridone, flurochloridone,
fluroxypyr, flurtamone, fluthiacet-methyl, fomesafen, glufosinate,
glyphosate, haloxyfop, hexazinone, imazamethabenz-methyl, imazamox,
imazapic, imazapyr, imazaquin, imazethapyr, indanofan, ioxynil,
isoproturon, isouron, isoxaben, isoxaflutole, isoxachlortole,
lactofen, lenacil, linuron, MCPA, MCPB, mecoprop, mecoprop-P,
mefenacet, mefluidide, mesotrione, metamitron, metazacilor,
methabenzthiazuron, methyldymron, metobenzuron, metobromuron,
metolachlor, S-metolachlor, metoxuron, metribuzin, molinate,
monolinuron, naproanilide, napropamide, naptalam, neburon,
norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon,
oxaziclomefone, oxyfluorfen, paraquat dichloride, pebulate,
pendimethalin, pentanochlor, pentoxazone, phemnedipham, picloram,
picolinafen, piperophos, pretilachlor, prodiamine, prometon,
prometryn, propachlor, propanil, propaquizafop, propazine, propham,
propisochlor, propyzamide, prosulfocarb, pyraflufen-ethyl,
pyrazolynate, pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate,
pyriftalid, pyriminobac-methyl, pyrithiobac, quinclorac, quinmerac,
quizalofop, quizalofop-P, sethoxydim, siduron, simazine, simetryn,
sulcotrione, sulfentrazone, 2,3,6-TBA, tebutam, tebuthiuron,
tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn,
thenylchlor, thiazopyr, thiobencarb, tiocarbazil, tralkoxydim,
tri-allate, triaziflam, triclopyr, trietazine, trifluralin and
vernolate. Illustrative herbicide safeners include benoxacor, BCS
(1-bromo-4-[(chloromethyl)sulfonyl]benzene), cloquintocet-mexyl,
cyometrinil, dichlormid, 2-(dichloromethyl)-2-methyl-1,3-dioxolane
(MG 191), fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim,
furilazole, isoxadifen-ethyl, mefenpyr-ethyl, methoxyphenone
((4-methoxy-3-methylphenyl)(3-methylphenyl)-methanone), naphthalic
anhydride and oxabetrinil. Of note are compositions where the mole
ratio of other active ingredients to sulfonamide herbicides is
between 1:100 and 100:1.
[0222] Of note are processes of this invention wherein the mixture
for extrusion comprises sulfometuron-methyl and a base comprising
sodium phosphate, or comprises thifensulfuron-methyl and a base
comprising sodium carbonate, or comprises tribenuron-methyl and a
base comprising sodium carbonate. Illustrating a combination of
inorganic bases, of further note is a process of this invention
wherein the mixture for extrusion comprises tribenuron-methyl and a
base comprising sodium carbonate and sodium phosphate. Also of note
are paste-extruded sulfonamide herbicide compositions prepared by
the processes of note.
[0223] The mixture for extrusion according to the process of this
invention may optionally contain up to 95%, typically from 5 to 70%
and often from 20 to 50% by weight on a water-free basis of
additives selected from wetting agents, dispersants, lubricants,
anticaking agents, chemical stabilizers and diluents. One skilled
in the art understands the purpose and selection of these
additives.
[0224] Wetting agents include but are not limited to alkyl
sulfosuccinates, laurates, alkyl sulfate and phosphate esters,
acetylenic diols, ethoxyfluorinated alcohols, ethoxylated
silicones, alkyl phenol ethoxylates, benzene sulfonates,
alkyl-substituted benzene sulfonates, alkyl .alpha.-olefin
sulfonates, napthalene sulfonates, alkyl-substituted napthalene
sulfonates, condensates of naphthalene sulfonates and
alkyl-substituted napthalene sulfonates with formaldehyde, and
alcohol ethoxylates. Of note are compositions comprising up to 10%
(e.g., from 0.1 to 5%) by weight of wetting agent on a water-free
basis. Compositions prepared according to the process of this
invention can comprise considerably greater amounts of wetting
agents (e.g., up to about 90 weight %) if the amounts of active
ingredient and base are correspondingly limited to accommodate the
amount of wetting agent.
[0225] Dispersants include but are not limited to sodium, calcium
and ammonium salts of ligninsulfonates (optionally
polyethoxylated); sodium and ammonium salts of maleic anhydride
copolymers; sodium salts of condensed phenolsulfonic acid; and
napthalene sulfonate-formaldehyde condensates. Of note are
compositions comprising up to 10% (e.g., from 0.1 to 5%) by weight
of dispersant on a water-free basis. Ligninsulfonates such as
sodium lignosulfonate are particularly useful for the process and
composition of the invention.
[0226] Lubricants include but are not limited to
polyvinylpyrrolidone, polyvinylalcohol and polyethylene oxide. They
have a median molecular weight greater than 50,000, a melt flow
temperature of at least 98.degree. C., and do not behave as
surfactants. Polyethylene oxide is preferred. Of note are
compositions comprising up to 3% (e.g., from 0.01 to 2%) by weight
of lubricant on a water-free basis. Higher levels are less
desirable, because they can slow the disintegration rate of the
granule.
[0227] Anticaking agents prevent clumping of granules, which could
occur during storage under hot warehouse conditions. Inorganic
bases such as sodium and ammonium phosphates used to provide base
equivalents may also help prevent clumping of granules. As referred
to herein, the term "anticaking agent" does not include inorganic
bases having conjugate acid pK.sub.as at least 2.1 units greater
than the highest pK.sub.a of the sulfonamide free acid component.
Anticaking agents include, but are not limited to, sodium and
ammonium phosphates not having conjugate acid pK.sub.as at least
2.1 units greater than the highest pK.sub.a of the sulfonamide free
acid component (e.g., sodium dihydrogen phosphate), sodium acetate,
magnesium hydroxide (all optionally hydrates), anhydrous calcium
chloride, molecular sieves, sodium alkylsulfosuccinates, calcium
and barium oxides. Of note are compositions comprising up to 10%
(e.g., from 0.1 to 5%) by weight of anticaking agent on a
water-free basis.
[0228] Chemical stabilizers prevent decomposition of active
ingredient during storage. Inorganic bases such as lithium, sodium
and potassium phosphates used to provide base equivalents may also
help prevent decomposition of active ingredient. As referred to
herein, the term "chemical stabilizer" does not include inorganic
bases having conjugate acid pK.sub.as at least 2.1 units greater
than the highest pK.sub.a of the sulfonamide free acid component.
Chemical stabilizers include, but are not limited to, lithium,
sodium and potassium phosphates not having conjugate acid pK.sub.as
at least 2.1 units greater than the highest pK.sub.a of the
sulfonamide free acid component (e.g., sodium dihydrogen
phosphate); sulfates of alkaline earth metals and transition metals
such as magnesium, zinc, aluminum and iron; calcium chloride and
oxide; and boric anhydride. Of note are compositions comprising up
to 10% (e.g., from 0.1 to 5%) by weight of chemical stabilizer on a
water-free basis.
[0229] Diluents, which include but are not limited to binders and
fillers, may be water-soluble or water-insoluble. Inorganic bases
such as alkali metal phosphates used to provide base equivalents
may also act as binders or fillers. As referred to herein, the term
"diluent" does not include inorganic bases having conjugate acid
pK.sub.as at least 2.1 units greater than the highest pK.sub.a of
the sulfonamide free acid component. The water-soluble diluents may
be, for example, salts or carbohydrates which dissolve rapidly in
water; non-limiting examples include alkali metal phosphates not
having conjugate acid pK.sub.as at least 2.1 units greater than the
highest pK.sub.a of the sulfonamide free acid component (e.g.,
sodium dihydrogen phosphate), alkaline earth phosphates, sulfates
of sodium, potassium, magnesium and zinc, sodium and potassium
chloride, sorbitol, sodium benzoate, lactose and sucrose.
Water-insoluble diluents include, but are not limited to clays,
synthetic and diatomaceous silicas, calcium and magnesium
silicates, titanium dioxide, aluminum, calcium and zinc oxide,
calcium and magnesium carbonate, sodium, potassium, calcium and
barium sulfate, and charcoal. Water-soluble diluents are preferred.
Of note are compositions comprising up to 85% (e.g., from 5 to 70%)
by weight of diluent on a water-free basis. Preferred as diluents
in the process and composition of the invention are saccharides,
including monosaccharides (e.g., glucose) and disaccharides (e.g.,
lactose, sucrose), in the amount of from about 0.5 to about 50% by
weight on a water-free basis. Disaccharides such as lactose and
sucrose are particularly preferred.
[0230] In preparing the mixture for extrusion, the other components
of the mixture are typically blended to form a homogeneous
composition before addition of water to make the mixture into an
extrudable paste. Of note is a solid composition (e.g., a powder)
comprising from 2 to 90% by weight on a water-free basis of one or
more active ingredients comprising at least one sulfonamide
herbicide free acid; from 0.5 to 94% by weight on a water-free
basis of a saccharide, preferably a disaccharide such as lactose or
sucrose; from 1 to 20% by weight on a water-free basis of
surfactant component preferably comprising a dispersant, for
example a ligninsulfonate dispersant (e.g., sodium lignosulfonate),
and optionally a wetting agent, for example a lauryl sulfate salt
(e.g., sodium lauryl sulfate); and at least about 50 equivalent %
of base selected from inorganic base equivalents having conjugate
acid pK.sub.as at least 2.1 units greater than the highest pK.sub.a
of the sulfonamide herbicide free acid component; wherein at least
10% of the sulfonamide herbicide content in the composition is in
free acid form. Said saccharide-containing solid composition may
optionally comprise additional ingredients; the sum of the weight %
of all the ingredients in said composition totaling 100% of a
water-free basis
[0231] Unmoistened homogeneous mixtures can be milled as necessary
to a form a powder for extrusion. The sizes of particles in the
powder for extrusion can vary considerably and still provide
according to the process of this invention an extruded sulfonamide
composition having good dispersibility, herbicidal efficacy and
spray equipment clean-out properties. Typically after milling, the
powder for extrusion has a mean particle size of less than about 60
microns (.mu.m), and at least 90% of the particles are less than
about 300 microns, wherein particle size is the equivalent
spherical diameter of the particle, i.e. the diameter of a sphere
enclosing the same volume as the particle. Milling using such
equipment as hammer mills typically can provide considerably finer
powders, which may increase the rate of dispersion or improve other
properties of the sulfonamide compositions prepared by the present
process. Mean particle size is the volume moment mean, also known
as the volume mean and the De Broucker mean, for the particles in
the powder for extrusion. With reference to particle size
distribution of the powder, percentages of particles are also on a
volume basis (e.g., "at least 90% of the particles are less than
about 300 microns" means that at least 90% of the aggregate volume
of particles consists of particles having equivalent spherical
diameters of less than about 300 microns). The principles of
particle size analysis are well known to those skilled in the art;
for a technical paper providing a summary, see A. Rawle, "Basic
Principles of Particle Size Analysis" (document MRK034 published by
Malvern Instruments Ltd., Malvern, Worcestershire, UK). Volume
distributions of particles in powders can be conveniently measured
by such techniques as Low Angle Laser Light Scattering (also known
as LALLS and Laser Diffraction), which relies on the fact that
diffraction angle is inversely proportional to particle size.
Commercially available instruments suitable for analyzing using
LALLS the volume distributions of particles in powders include the
Mastersizer 2000 (Malvern Instruments). Preferred is the process of
this invention in which the powder for extrusion has a mean
particle size of less than about 30 microns, more preferably less
than about 20 microns and most preferably less than about 15
microns, and in which at least 90% of the particles are less than
about 100 microns, more preferably less than about 40 microns and
most preferably less than about 30 microns. Alternatively, milling
of components may be done separately prior to incorporation into
the mixture. In some cases, it is sufficient to mill only the water
insoluble components. Suitable mills include, but are not limited
to, lab-scale high-speed rotary mills, such as a Techmar.RTM. A10
Analytical Mill, and commercial-scale hammer mills and air
classifying mills, such as those manufactured by Hosokawa Micron
Powder Systems, Summit, N.J.
[0232] To make the mixture suitable for extrusion, water is added
to form an extrudable paste. The mixture of dry components is
typically added to a low to moderate shear mixer, or kneader,
wetted with water and mixed until an extrudable paste is obtained.
Water may be added either as a spray or as a stream. Typically, 5
to 50% water based on the weight of dry component mixture (i.e. 5
to 50 parts of water to 100 parts by weight of dry component
mixture) is required to produce an extrudable paste. Alternatively,
water-soluble ingredients may be added to the water. Water-soluble
ingredients that may be added include, for example but not
limitation, other volatile solvents such as lower molecular weight
alcohols (e.g., methanol, ethanol and isopropanol) as well as
nonvolatile formulating ingredients described above (e.g., wetting
agents, dispersants, lubricants, anticaking agents, chemical
stabilizers and diluents) that are water soluble. Also, part or all
of the inorganic base equivalents in the mixture can be first
dissolved in the water. Typically the added water does not contain
water-soluble ingredients other than impurities commonly found in
tap (i.e. potable) water. Suitable mixers include, but are not
limited to, food processors, sigma arm mixers (such as a
"Kneadermaster" manufactured by The Patterson Foundry & Machine
Co., East Liverpool, Ohio), pug mixers and continuous kneaders
(such as those available from LCI Corporation, Charlotte,
N.C.).
[0233] Extrusion is accomplished by passing the paste through a
paste extruder to produce extrudate (a wet extruded strand).
Examples of paste extruders include, but are not limited to, basket
extruders, radial extruders and dome extruders; such as available
from LCI Corporation, Charlotte, N.C. The extruder is fitted with a
die, or screen, with hole diameters typically from 0.3 to 3 mm,
preferably 0.5 to 1.5 mm and most preferably 0.7 to 1.0 mm.
[0234] The extrudate is then dried. A wide variety of drying
methods can be used to dry the extrudate. Conventional drying
methods include tray, rotary, fluidized bed and vibrating fluidized
bed. Drying methods that subject the extrudate to vibration,
tumbling or other forms of agitation will also serve to break the
extruded strand into shorter lengths and ultimately into granules
that can be dispensed by volumetric measurement. Fluidized bed
drying is preferred, as fluidization will increase fracture of the
drying extruded strand by impact into discrete granules. Most
preferred is vibrating fluidized bed drying. Drying to moisture
levels less than 5% (preferably less than 3%) as measured by a
moisture balance, such as available from Mettler, Inc., Toledo,
Ohio, produces hardened granules without tack. Hardened, non-tacky
granules are preferred, because they have reduced tendency to
agglomerate. Drying temperatures greater than about 40.degree. C.,
preferably at least 60.degree. C. but not exceeding 110.degree. C.
and typically not exceeding 90.degree. C., efficiently produce the
required moisture levels.
[0235] Prior to packaging and use, the dried extruded granules are
typically sifted to remove fines and any agglomerated chunks, as
well as possibly break the extruded granules into shorter lengths.
Accordingly, the process of this invention may further comprise a
step of sifting the dried extrudate. Compositions of granules with
lengths suitable for dispensing by volumetric measurement can be
obtained by breaking the dried granules using sifting to obtain
length distributions from about 0.3 to about 7 mm, preferably from
about 0.5 to about 5 mm and most preferably from about 0.7 to about
4 mm. Alternatively the dried granules can be broken using a rotary
sifter as described in U.S. Pat. No. 6,270,025 to produce length
distributions that are especially suitable for preparing
homogeneous blends as described in U.S. Pat. No. 6,022,552.
[0236] Besides having significantly improved spray tank clean out
properties, formulations prepared from mixtures containing at least
about 50 equivalent % of a base according to the process of this
invention have also been discovered to provide substantially better
control of weeds under certain circumstances than comparison
formulations prepared from mixtures containing lesser amounts or no
base. Because weed control has a limit of 100%, better weed control
by formulations of this invention are most apt to be realized under
circumstances where said comparison formulations provide much less
than 100% control. These circumstances include treatment of
hard-to-control weed species, which may be only suppressed instead
of efficiently controlled by said comparison formulations. The
improved herbicidal efficacy of formulations of this invention may
also be realized in controlling otherwise relatively
easy-to-control weed species at low application rates for which
said comparison formulations provide only suppression. Other
circumstances where formulations of this invention may provide
significantly improved weed control include applications using
relatively small spray volumes. Formulations of the present
invention may obviate need to add to the spray liquid supplementary
surfactants besides those included in the formulation, although
adding such surfactants may also benefit weed control by
formulations of the present invention.
[0237] Without further elaboration, it is believed that one skilled
in the art using the preceding description can utilize the present
invention to its fullest extent. The following Examples are,
therefore, to be construed as merely illustrative and not limiting
of the disclosure in any way whatsoever.
ANALYTICAL EXAMPLES
Analytical Example 1
Illustrative Procedure for Determining pK.sub.a of a Sulfonamide
Herbicide
[0238] A stock buffer solution is prepared by dissolving sodium
acetate trihydrate (6.8 g), sodium phosphate dodecahydrate (19.0 g)
and sodium borate decahydrate (19.1 g) in highly purified water
(500 mL). This stock buffer solution is typically diluted 100-fold
with highly purified water to give a 0.001 M test buffer solution
having a pH between pH 9 and pH 10. If necessary, a stronger
concentration of the buffer can be prepared. A stock solution of
the sulfonamide herbicide free acid is prepared in an organic
solvent, preferably a solvent miscible with water such as acetone.
The concentration of the stock solution should not exceed the
lesser of 1 M or half the saturation concentration for the organic
solvent used.
[0239] A UV/visible light spectrophotometer equipped with
temperature control capable of maintaining temperature at the test
temperature (e.g., 20.degree. C.) is used to record spectra for the
sulfonamide at various pHs. The 0.001 M test buffer solution is
used as a blank. Spectra are recorded for aliquots of the
sulfonamide stock solution added to a hydrochloric acid solution
(pH .ltoreq.2) and sodium hydroxide solution (pH .gtoreq.10),
respectively. The optimal analytical wavelength, where the acidic
and basic (salt) forms of the sulfonamide differ appreciably in
absorbance from one another is noted and used for the subsequent
analysis. An aliquot of the stock sulfonamide solution is added to
a flask and the solvent evaporated under nitrogen. Buffer solution
(0.001 M, 100 mL) is added to the flask, and the mixture is
magnetically stirred to form the test solution. The pH is recorded
using a calibrated pH meter capable of resolving differences of 0.1
pH units or less. The pH of the test solution is adjusted to
approximately pH 2 using hydrochloric acid, and then sodium
hydroxide solution is added in increments to obtain about 0.5 or
less pH-units of change per increment up to pH of 10 to 12, and the
UV/visible absorbance is recorded as a function of change in pH at
the analytical wavelength. Regression analysis based on a
nonlinear, least-squares model for a plot of absorbance versus pH
is performed to determine the pH at which the sulfonamide free acid
and sulfonamide salt are present in equimolar amounts; this pH is
the pK.sub.a of the sulfonamide. The test is preferably replicated
to ensure accuracy.
Analytical Example 2
Illustrative Procedure for Determining Solubility of a Sulfonamide
Herbicide in pH 7 Buffer
[0240] A stock pH 7 buffer solution is prepared by adding aqueous
sodium hydroxide solution (0.1 M, 145 mL) to aqueous potassium
dihydrogen phosphate solution (0.1 M, 250 mL), and then adding
sufficient distilled water to adjust the final volume to 500 mL. At
least 1 times up to about 5 times the amount of sulfonamide needed
for saturation is added to a mixing vessel containing stock buffer
solution at the test temperature (e.g., 20.degree. C.). The mixture
is magnetically stirred in the dark while being maintained at the
test temperature. Samples are periodically removed for analysis.
The samples are centrifuged using a high speed,
temperature-controlled centrifuge at the test temperature for about
20 minutes at .gtoreq.12000 G to remove suspended particles. An
aliquot of each supernatant is taken for analysis.
[0241] The concentration of sulfonamide in the supernatant is
determined by a high pressure liquid chromatography (HPLC) method
suitable for the particular sulfonamide. Typically the HPLC method
will use a reversed phase chromatography column and UV detection.
The method should include development of best-fit calibration
curves based on at least three standards using linear regression
analysis. Also, the pH of the supernatant is measured using a
calibrated pH meter capable of resolving differences of 0.1 pH
units or less to verify that the pH is 7. Samples are successively
withdrawn from the mixing vessel and analyzed until three
successive samples show little or no variation in concentration.
The test is preferably replicated to ensure accuracy.
FORMULATION PROCESS EXAMPLES
[0242] Formulations were prepared by combining ingredients in the
indicated percentages to make from 20 to 50 grams of unmoistened
mixture. Unless otherwise noted, formulations contained 50% of
sulfonamide herbicide, 0.5% Supralate.RTM. ME Dry (sodium lauryl
sulfate, marketed by Witco Inc., Greenwich, Conn.), 5% Reax.RTM.
88B (sodium lignosulfonate, marketed by Westvaco Corp., N.
Charleston Heights, S.C.), and an inorganic base at an amount to
give the indicated equivalent of base (relative to the sulfonamide
herbicide) in the final composition. The balance of the formulation
composition was sucrose and/or lactose monohydrate. The mixture was
blended and milled in a high-speed rotary mill. The milled mixture
(from 10 to 15 g) and water (from 2 to 5 mL) were combined using as
mixer the rotary mill at low speed to form a paste, which was then
extruded through a 1.0 mm die. The wet extrudate was dried at
70.degree. C. in a vacuum oven and then sifted through 0.71-2 mm
screens to obtain the product granules. The compositions of the
example formulations are summarized in Table 1. TABLE-US-00003
TABLE 1 Summary of Example Formulations Sulfonamide herbicide
Sulfonamide Supralate Reax 88B Sucrose Lactose (*) Base Ex.
ingredient amt. (%) ME (%) (%) (%) (%) Base ingredient (%) 1
Thifensulfuron-methyl 50.0 0.5 5.0 1.0 43.5 None -- 2
Thifensulfuron-methyl 50.0 0.5 5.0 1.0 34.5 Na.sub.2HPO.sub.4 9.0 3
Thifensulfuron-methyl 50.0 0.5 5.0 1.0 6.5 Na.sub.2HPO.sub.4 37.0 4
Thifensulfuron-methyl 50.0 0.5 5.0 1.0 36.5 K.sub.3PO.sub.4 7.0 5
Thifensulfuron-methyl 50.0 0.5 5.0 1.0 16.5 K.sub.3PO.sub.4 27.0 6
Thifensulfuron-methyl 50.0 0.5 5.0 1.0 40.1 Na.sub.2CO.sub.3 3.4 7
Thifensulfuron-methyl 50.0 0.5 5.0 1.0 29.5 Na.sub.2CO.sub.3 14.0 8
Thifensulfuron-methyl 50.0 0.5 5.0 1.0 36.5 KHCO.sub.3 7.0 9
Thifensulfuron-methyl 50.0 0.5 5.0 1.0 17.5 KHCO.sub.3 26.0 10
Sulfometuron-methyl 50.0 0.5 5.0 3.0 41.5 None -- 11
Sulfometuron-methyl 50.0 0.5 5.0 3.0 38.6 Na.sub.3PO.sub.4 (**) 2.9
12 Sulfometuron-methyl 50.0 0.5 5.0 3.0 35.9 Na.sub.3PO.sub.4 (**)
5.6 13 Sulfometuron-methyl 50.0 0.5 5.0 3.0 30.1 Na.sub.3PO.sub.4
(**) 11.4 14 Sulfometuron-methyl 50.0 0.5 5.0 3.0 19.1
Na.sub.3PO.sub.4 (**) 22.4 15 Sulfometuron-methyl 36.5 0.4 3.6 2.2
24.5 Na.sub.3PO.sub.4 (**) 32.8 16 Sulfometuron-methyl 50.0 0.5 4.0
0.0 0.5 Na.sub.3PO.sub.4 45.0 17 Bensulfuron-methyl 50.0 0.5 5.0
0.0 44.5 None -- 18 Bensulfuron-methyl 50.0 0.5 5.0 0.0 41.1
Na.sub.2CO.sub.3 3.4 19 Bensulfuron-methyl 50.0 0.5 5.0 0.0 37.8
Na.sub.2CO.sub.3 6.7 20 Bensulfuron-methyl 50.0 0.5 5.0 0.0 31.5
Na.sub.2CO.sub.3 13.0 21 Bensulfuron-methyl 50.0 0.5 5.0 0.0 18.5
Na.sub.2CO.sub.3 26.0 22 Tribenuron-methyl 50.0 0.5 5.0 0.0 44.5
None -- 23 Tribenuron-methyl 50.0 0.5 5.0 0.0 37.8 Na.sub.2CO.sub.3
6.7 24 Tribenuron-methyl 50.0 0.5 5.0 0.0 18.0 Na.sub.2CO.sub.3
26.5 (*) Weight percentage also includes water of hydration and
technical impurities in the formulations. (**) Na.sub.3PO.sub.4 was
added in the form of the dodecahydrate, but the listed amount is
calculated based on the anhydrous equivalent.
[0243] The granular compositions were evaluated by the following
clean-out test procedure determines the sulfonamide herbicide
residue that could potentially remain in organic sits in a spray
tank.
Laboratory Clean-Out Test Procedure
[0244] The test was conducted by dispersing in water a sample of
the granular composition to produce a concentration that is
normally used when applying the herbicide: 600 ppm for
thifensulfuron-methyl and 350 ppm for sulfometuron-methyl,
bensulfuron-methyl and tribenuron-methyl. The appropriate amount of
the granules was added to tap water (300 mL) in a 400-mL beaker and
magnetically stirred for 2 minutes. After stirring, Tilt.RTM. 250
(1.5 mL, propiconazole formulation, commercially available from
Syngenta, Basil, Switzerland) was added. The mixture was then
stirred for an additional 2 minutes, whereupon the resulting
dispersion was dispensed in three 100-mL aliquots to 4-oz (118-mL)
polyethylene bottles. The bottles were capped, inverted twice and
allowed to stand overnight.
[0245] After standing overnight, each individual bottle was
inverted twice and the liquid contents were then poured out. Tap
water (10 mL) was added and the bottle was inverted until all
sediment was re-suspended, whereupon the contents were poured out.
Tap water (100 mL) was added and the bottle was inverted twice and
then allowed to stand undisturbed for 10 minutes. The bottle was
inverted twice more and the contents were poured put. Acetonitrile
(10 mL) was added to the bottle to extract any remaining material.
The acetonitrile solution was analyzed by reversed-phase liquid
chromatography with UV detection. The cleanout rating (the
concentration of sulfonamide herbicide in the acetonitrile
solution) is reported in ppm in Table 2 below. Lower cleanout
ratings indicate more effective cleanout compared to higher
ratings. The clean-out test was repeated twice for formulation
examples 1, 10 and 17, which contained no base, and the two sets of
results are separately listed. TABLE-US-00004 TABLE 2 Summary of
Formulations Evaluated Using Clean-Out Test Approx. Equivalent %
Sulfonamide herbicide Sulfonamide Base Base Relative Cleanout
Rating Ex. ingredient amt. (%) Base ingredient (%) to S.U. (as ppm
S.U.) 1 Thifensulfuron-methyl 50.0 None -- 0 203, 150 2
Thifensulfuron-methyl 50.0 Na.sub.2HPO.sub.4 9.0 49 2 3
Thifensulfuron-methyl 50.0 Na.sub.2HPO.sub.4 37.0 202 0 4
Thifensulfuron-methyl 50.0 K.sub.3PO.sub.4 7.0 51 66 5
Thifensulfuron-methyl 50.0 K.sub.3PO.sub.4 27.0 197 4 6
Thifensulfuron-methyl 50.0 Na.sub.2CO.sub.3 3.4 50 9 7
Thifensulfuron-methyl 50.0 Na.sub.2CO.sub.3 14.0 204 0 8
Thifensulfuron-methyl 50.0 KHCO.sub.3 7.0 54 3 9
Thifensulfuron-methyl 50.0 KHCO.sub.3 26.0 201 0 10
Sulfometuron-methyl 50.0 None -- 0 280, 310 11 Sulfometuron-methyl
50.0 Na.sub.3PO.sub.4 2.9 13 280 12 Sulfometuron-methyl 50.0
Na.sub.3PO.sub.4 5.6 25 270 13 Sulfometuron-methyl 50.0
Na.sub.3PO.sub.4 11.4 50 290 14 Sulfometuron-methyl 50.0
Na.sub.3PO.sub.4 22.4 99 50 15 Sulfometuron-methyl 36.5
Na.sub.3PO.sub.4 32.8 197 1 16 Sulfometuron-methyl 50.0
Na.sub.3PO.sub.4 45.0 198 2 17 Bensulfuron-methyl 50.0 None -- 0
330, 190 18 Bensulfuron-methyl 50.0 Na.sub.2CO.sub.3 3.4 26 190 19
Bensulfuron-methyl 50.0 Na.sub.2CO.sub.3 6.7 51 220 20
Bensulfuron-methyl 50.0 Na.sub.2CO.sub.3 13.0 100 120 21
Bensulfuron-methyl 50.0 Na.sub.2CO.sub.3 26.0 199 6 22
Tribenuron-methyl 50.0 None -- 0 70 23 Tribenuron-methyl 50.0
Na.sub.2CO.sub.3 6.7 50 5 24 Tribenuron-methyl 50.0
Na.sub.2CO.sub.3 26.5 198 0
[0246] Formulation Examples 1, 10, 17 and 22 illustrate
conventional paste-extruded granular sulfonamide herbicide
compositions containing little or no inorganic base. As can be seen
from the data in Table 2, granular compositions prepared according
to the process of this invention to contain about 50 equivalent
percent of base resulted in much lower sulfonamide herbicide levels
recovered in the acetonitrile wash solution when the sulfonamide
herbicide was thifensulfuron-methyl; sodium carbonate was
particularly efficacious on a % weight basis in the process of this
invention to produce a thifensulfuron-methyl composition with low
residue. For tribenuron-methyl 50 equivalent percent of base
achieved a very substantial effect. For sulfometuron-methyl and
bensulfuron-methyl, around 100 equivalent percent of base was
needed to achieve a substantial effect, and increasing the amount
of base to around 200 equivalent percent reduced the residue to
negligible levels. This indicates that granular compositions
prepared according to the process of this invention can result in
significantly lower sulfonamide herbicide residues in spray
equipment.
HERBICIDE TEST EXAMPLES
Formulation Preparation
[0247] Samples of formulations of Examples 1, 5 and 7
(thifensulfuron-methyl) and Examples 22 and 24 (tribenuron-methyl)
were prepared according to the procedure described above in the
Formulation Process Examples section.
Greenhouse Bioassay
[0248] The different formulations of thifensulfuron-methyl and
tribenuron-methyl were evaluated in separate tests on Convolvulus
arvensis L. (field bindweed) and Galium aparine L. (catchweed
bedstraw). Both species were planted approximately 1 to 2 cm deep
in 15-cm plastic pots. Convolvulus arvensis was thinned after
emergence to two plants, and Galium aparine was thinned to three
plants. Pots contained a synthetic growth medium (Redi-Earth.RTM.
potting media, Scotts-Sierra Horticultural Products Company,
Marysville, Ohio 43041) and were watered and fertlized for rapid
growth. Metal halide lights providing 160 .mu.E/m.sup.2/s
photosynthetically active radiation supplemented natural intensity
during a 16-h photoperiod when light intensity was below 500
.mu.E/m.sup.2/s. Day temperature was 28.+-.2.degree. C. and night
temperature was 22.+-.2.degree. C. Convolvulus arvensis and Galium
aparine were each grown for 19 days and selected for uniformity
before spraying. Plant heights of Convolvulus arvensis and Galium
aparine were 10 to 13 cm and 4 to 6 cm, respectively.
[0249] Spray mixtures were made with deionized water at room
temperature. Treatments were sprayed in a 94 L/ha volume
approximately one hour after preparation. Treatments were
replicated four times and were applied with a flat fan nozzle
(TeeJet.RTM. flat-fan SS8001E model, Spraying Systems Co., Wheaton,
Ill. 60188) at 51 cm height with spray pressure set at 138 kPa. The
surfactant ceteareth-25 (polyethylene glycol ether of cetearyl
alcohol (mixture of cetyl and stearyl alcohols) containing an
average of 25 ethylene glycol units) was used at 0.1% of the spray
volume where indicated. Plant shoots were weighed 15 days after
treatment, and fresh weight inhibition was compared with untreated
plants. The means, expressed as percent inhibition, are listed in
Table 3. TABLE-US-00005 TABLE 3 Comparison of the activity of
thifensulfuron-methyl and tribenuron-methyl formulations on
Convolvulus arvensis and Galium aparine with and without 0.1% w/w
nonionic surfactant, ceteareth-25. Rate % Con- (g a.i./ Formu-
Nonionic volvulus % Galium Herbicide ha) lation Surfactant
Inhibition Inhibition Thifensulfuron- 15 Ex. 1 None 35 87 methyl
Ceteareth-25 84 97 Ex. 5 None 72 89 Ceteareth-25 91 98 Ex. 7 None
69 88 Ceteareth-25 94 96 45 Ex. 1 None 61 94 Ceteareth-25 89 97 Ex.
5 None 79 92 Ceteareth-25 94 99 Ex. 7 None 78 96 Ceteareth-25 95 98
Tribenuron- 15 Ex. 22 None 81 61 methyl Ceteareth-25 88 92 Ex. 24
None 84 83 Ceteareth-25 90 94 45 Ex. 22 None 78 90 Ceteareth-25 92
96 Ex. 24 None 89 91 Ceteareth-25 93 96
[0250] As can be seen from the results shown in Table 3, the
paste-extruded thifensulfuron-methyl formulations prepared from
mixtures containing base according to the process of this invention
(i.e. Formulation Examples 5 and 7) provided much better control of
Convolvulus arvensis than did the comparison formulation prepared
from a mixture without added base (i.e. Formulation Example 1).
While adding the surfactant ceteareth-25 to the spray solution
enhanced the efficacy of comparison Formulation Example 1, the
surfactant also further increased the efficacy of Formulation
Examples 5 and 7, so that the best results in controlling
Convolvulus arvensis were obtained from using ceteareth-25 with
Formulation Examples 5 and 7 prepared according to the process of
this invention. Also as can been seen from the results shown in
Table 3, the paste-extruded tribenuron-methyl formulations prepared
from mixtures containing base according the process of this
invention (i.e. Formulation Example 24) provided much better
control of Convolvulus arvensis at both application rates tested,
and also much better control of Galium aparine at the lower (15 g
a.i./ha) application rate than did the comparison formulation
prepared from a mixture without added base (i.e. Formulation
Example 22). The efficacy of both tribenuron-methyl formulations
was increased by adding the surfactant ceteareth-25 to the spray
solutions. In this bioassay experiment the formulations prepared
according to the process of this invention showed the greatest
advantage on weeds not well controlled by the comparison
formulations at the application rates tested. These results
demonstrate another remarkable benefit besides improved spray
equipment clean-out properties for formulations prepared according
to the process of the present invention.
* * * * *